PRECURSORS FOR COPPER CHEMICAL VAPOR DEPOSITION

A Dissertation

Submitted to the Graduate Faculty of the

Louisiana State University and
Agricultural and Mechanical College
in partial fulfilment
of the requirements for the degree of
Doctor of Philosophy
in

The Department of Chemistry

by
Muna BuFaroosha
B.S. United Arab Emirates University, 1989
M.S. Michigan State University, 1995
August, 2002

Acknowledgment

This degree was my only dream and Dr. Maverick made it come true.

ii

Table of Contents
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
Lists of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
Lists of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Metallization Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Copper Metallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 CVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5 Precursors For Cu-CVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.6 Cu(hfac)2(alcohol) Adducts As Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.7 Cu(hfac)2(amine) Adducts As Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.8 Tetrameric Copper(I)-Amide Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Chapter 2 Cu(hfac)2 Adducts With Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.1.1 General Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.2 Cu(hfac)2(dimethylamine) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.3 Cu(hfac)2(pyrrolidine) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.4 Other Amine Adducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2.5 Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2.6 CVD Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.3 Results And Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.3.1 Thermodynamic Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.3.2 Synthesis And Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.3 CVD Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.3.1 Cu(hfac)2(H2O) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.3.2 Amine Adducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.5 Film Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.3.6 Adhesion Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

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Chapter 3 Attempted Synthesis Of Other Cu(hfac)2(amine) Adducts . . . . . . . . . 33

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2.1 Reaction of Cu(hfac)2 With Triethylamine . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2.2 (HNEt3)[Cu(hfac)3].H2O . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.2.3 Reaction Of Cu(hfac)2 With Quinuclidine . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2.4 Reaction Of Cu(hfac)2 With Diethylamine . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.2.5 Reaction Cu(hfac)2 With Diisopropylethylamine . . . . . . . . . . . . . . . . . . . . 37
3.2.6 Attempted Synthesis Of Cu(hfac)2(propylene glycol)2 . . . . . . . . . . . . . . . . 38
3.2.7 X-ray Structure Determinations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.3 Results And Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3.1 Reactions Of Cu(hfac)2 With Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3.1.1 Reactions Of Cu(hfac)2 With Triethylamine . . . . . . . . . . . . . . . . . . . . . . 41
3.3.1.2 Structure Of New Cu(II) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3.1.3 Reaction Of Cu(hfac)2 With Diisopropylethylamine . . . . . . . . . . . . . . . 43
3.3.2 Cu(hfac)2 And Propylene Glycol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Chapter 4 Terameric Copper(I) Amide Clusters . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.2.1 [CuN(SiMe3)2]4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.2.2 [CuN(t-Bu)(SiMe3)]4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2.3 [CuN(i-Pr)2]4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.2.4 [CuNEt2]4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2.5 Luminescence Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3.1 Preparation And Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3.1.1 Structure Of Related Tetramers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.3.2 Phosphorescence Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.4.1 Spectroscopic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Chapter 5 Conclusions and Future Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.2 Cu(hfac)2(amine) Adducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.3 [CuNR2]4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.4 Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Appendix A Crystal Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70

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Appendix B Phosphorescence Spectra of Cu(I) Amides . . . . . . . . . . . . . . . . . . 242

Vita . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

List of Tables
Table 1.1 Features Of Representative Copper Precursors . . . . . . . . . . . . . . . . . . . 8
Table 2.1 CVD Of Cu(hfac)2 With NH3 As The Carrier Gas . . . . . . . . . . . . . . . 15
Table 2.2 Elemental Analysis Of Cu(hfac)2(amine) Adducts . . . . . . . . . . . . . . . 19
Table 2.3 Crystal Data Collection Parameters For Cu(hfac)2(pyrrolidine) And
Cu(hfac)2(dimethylamine) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Table 2.4 Film Thickness And Resistivity Of One Cu Film Deposited
From Cu(hfac)2(dimethylamine) Under Hydrogen . . . . . . . . . . . . . . . . . . . . . . . 24
Table 2.5 Enthalpies Of Dehydrogenation Of Some Amines . . . . . . . . . . . . . . . 25
Table 2.6 CVD Results Under H2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Table 2.7 CVD Results Under N2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Table 2.8 Adhesion Test Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Table 3.1 Crystal Data And Collection Parameters . . . . . . . . . . . . . . . . . . . . . . . 40
Table 3.2 Elemental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Table 3.3 CVD Results Using Cu(hfac)2(i-PrOH) . . . . . . . . . . . . . . . . . . . . . . . . 47
Table 4.1 Crystal Data For [CuN(t-Bu)(SiMe3)]4 . . . . . . . . . . . . . . . . . . . . . . . . 55
Table 4.2 Luminescence Of Cu(I) Tetramers and their Stability . . . . . . . . . . . . 57
Table 4.3 Estimated 8em max For Phosphorescence (nm) . . . . . . . . . . . . . . . . . . 58
Table 4.4 Structural Parameters Of Cu(I) Amido Tetramers . . . . . . . . . . . . . . . . 58
Table 4.5 Solid State Emission Maxima . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

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List of Figures
Figure 1.1 PVD (right) Has Limited Conformal Coverage Compared to
CVD (left) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Figure 1.2 Schematic Diagram Of A Damascene Process . . . . . . . . . . . . . . . . . . 6
Figure 1.3 CVD Process Steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Figure 1.4 Structure Of Cu(hfac)(tmvs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Figure 1.5 The Structure Of Cu(II) $-diketonates . . . . . . . . . . . . . . . . . . . . . . . . 9
Figure 2.1 Precursors For Copper CVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Figure 2.2 ORTEP Drawing Of Cu(hfac)2(dimethylamine) . . . . . . . . . . . . . . . . 20
Figure 2.3 ORTEP Drawing Of Cu(hfac)2(pyrrolidine) . . . . . . . . . . . . . . . . . . . 21
Figure 2.4 Depiction Of Cu CVD Film Measurement . . . . . . . . . . . . . . . . . . . . . 23
Figure 3.1 ORTEP Drawing Of [Et3NH][(hfac)2Cu(:-OH)Cu(hfac)2] . . . . . . . . 34
Figure 3.2 ORTEP Drawing Of (Et3NH)[Cu(hfac)3].H2O . . . . . . . . . . . . . . . . . . 35
Figure 3.3 ORTEP Drwing Of The Dianion [Cu3(hfac)6(OH)2]-2 From
The Structure Of (quinuclidinium)[Cu3(hfac)6(OH)2] . . . . . . . . . . . . . . . . . . . . 36
Figure 3.4 ORTEP Drawing Of
trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2 . . . . . . . . . . . . . . . . . . . . 37
Figure 3.5 ORTEP Drawing Of [(hfac)Cu(:3-OCH2CH(OH)CH3)]4 . . . . . . . . . 39
Figure 3.6 The Delocalized Structure Of
2,4-dichloro-1-diethylamino-3,5-diphenyl-1,3-pentadien-5-one . . . . . . . . . . . . . 45
Figure 3.7 Cubane Structure Of [(hfac)Cu(:3-OR]4 . . . . . . . . . . . . . . . . . . . . . . 48
Figure 4.1 ORTEP Drawing of [CuN(t-Bu)(SiMe3)]4 . . . . . . . . . . . . . . . . . . . . . 54
Figure 4.2 The Separation Between Cu...Cu is Affected by the Ligand Type. . . 59
Figure 4.3 MO Diagram for [CuN(SiH3)]4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

vii

Figure 4.4 Two M-M Bonding Contributions to the LUMO in [CuN(SiH3)]4

Combinations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

viii

Abstract
The main objective of this study was to synthesize precursors that are capable of
producing copper films of high quality by chemical vapor deposition (CVD). We
investigated some copper(I) and copper(II) complexes as precursors for chemical or
photochemical vapor deposition.
In chapter 2, we synthesized a series of Cu(hfac)2(amine) adducts, where hfac is
hexafluoroacetylacetonate and the amines are: dimethylamine, isopropylamine,
allylamine, pyrrolidine, and piperidine. The efficiency of these adducts compared to
Cu(hfac)2(H2O) as Cu-CVD precursors was examined under hydrogen. We found that
among these amine adducts, Cu(hfac)2(allylamine)2 gave the best deposition rate under
hydrogen. Their capability as self reducing precursors was tested under the inert gas
nitrogen. All the amine adducts in this study deposited copper films under nitrogen,
which demonstrated their ability as self reducing precursors. All the amine adducts
except Cu(hfac)2(allylamine)2 exhibited square pyramidal geometry where the hfac
ligand twists out of the plane permitting one of the CuO bonds to take the apical
position.
Chapter 3 summarizes the reactions of Cu(hfac)2 and certain amines which
resulted in compounds with formulas other than Cu(hfac)2L. Here we learned that the
reaction between Cu(hfac)2 and NEt3 does not afford the adduct Cu(hfac)2(NEt3) as
reported in the literature. The species that we were able to isolate from this reaction
indicate that this reaction is not a simple adduct formation but possibly proceeds via
proton transfer. In general we concluded from the work presented in this chapter that

ix

bulky amines give different adducts than the desired Cu(hfac)2(amine).

The second class that we attempted to examine as copper precursors for chemical
or photochemical vapor deposition was the Cu(I)-amide clusters. In chapter 4 we
studied the photoactivities of a series of these tetramers: [CuN(SiMe3)2]4,
[CuN(t-Bu)(SiMe3)]4, [CuNEt2]4, and [CuN(i-Pr)2]4. We studied their lowest-energy
excited states by measuring their phosphorescence spectra. We found that these
tetramers behave similarly when it comes to their absorption and emission of light.

Chapter 1
Introduction
Recently, copper chemical vapor deposition (CVD) has received great
recognition in the industrial and academic area. This attention arose as the result of the
need for new interconnect materials that could overcome limitations that had been
attributed to aluminum (Al), the currently used interconnect material. For some time
now, our research group has been studying the development of new copper containing
metallization materials.
What follows here is a general background description of copper CVD along
with a brief description of the current technologies and techniques utilized in this area
of ongoing research.
1.1 Metallization Technology
Metals are used to connect the miniature components on silicon wafers in
integrated circuits (ICs). These interconnects both supply power and transmit
information.1.1 Technological advances in the area of submicron IC device fabrication
have created the need for the industry to design downscaled devices,1.2 among which are
dynamic random access memory (DRAM), static random access memory (SRAM), and
electrically erasable and programmable read only memory (EEPROM).1.3
The physical and chemical properties of aluminum (Al) are compatible with
large scale integration (LSI) processing. This has enabled the industry to widely use
aluminum or aluminum alloy as the interconnect materials in LSI circuits. For example,
aluminum is an inexpensive material with low electrical resistivity (2.7 S cm), and it

forms a thin protective oxide film that withstands the various thermal processes that
take place during circuit fabrication. The reliability of aluminum, nonetheless, poses a
major concern for maintaining the total reliability of advanced LSI. In essence, the low
melting point of aluminum (660 C) makes it prone to stress-induced voidage and
electromigration, which can lead to failure of the interconnect. The speed at which
these forms of failure occur is increased by decreasing the width and thickness of the
interconnects. As a result, industrial applications of Al interconnects may be limited for
ICs with feature sizes below 0.25 :m.1.2,1.4
Improved LSI performance and reliability require wiring manufactured from
materials that have lower resistivity and higher resistance to electromigration than Al
alloys. Gold, copper, and silver have lower resistivity than Al and thus are candidate
wiring materials. However, these three metals cannot be used in direct contact with
silicon (Si), primarily because all three form deep levels in the bandgap of silicon,
which interferes with transistor performance. While silver (Ag) displays severe
migration problems, both gold and copper exhibit similar material properties and
processing problems. Gold films with low resistivities made by hydrogen plasmaassisted CVD have been achieved. The lower resistivity of copper, nonetheless, is an
advantage compared with gold. Even though some ICs already contain copper
interconnects, industry will continue to use both aluminum (Al) and tungsten (W) for
local interconnects, the latter because of its high electromigration resistance which
offsets its higher electrical resistivity.1.3

1.2 Copper
To overcome the limitations imposed by aluminum interconnects, and since
copper has a higher melting point (1085 C) and lower resistivity (1.67 S cm) than
aluminum, copper wiring technology is now being adopted as an interconnect
material.1.4
Electromigration can be defined as the motion of atoms in a metallic conductor
caused by the passage of current. Atoms move in the direction of the electron drift
causing the cathodic end of the wire to be consumed. This can lead to such damage as
openings in the lines or shorts to adjacent lines. This damage is made worse by
inhomogeneity in the interconnect, which leads to excessive local heating.1.5,1.6
For the same size of interconnect, the time to failure by copper electromigration
is approximately two orders of magnitude higher than that of aluminum. The amount of
time that it takes for a circuit to fail is dependent on current density. Therefore, the
maximum allowable current density of copper (105 A/cm2) is about two orders of
magnitude higher than that of aluminum.1.3
1.3 Copper Metallization
There are major challenges in the implementation of copper in actual silicon LSI
devices. Copper is not compatible with some of the other materials used in ICs. For
example, copper readily diffuses into silicon dioxide and silicon substrates under the
high temperatures reached in device manufacture. At deposition temperatures, copper
may interact with silicon which may result in the formation of copper silicides and
copper-doped silicon. Additionally, in the standard metallization procedure, plasma

etching is applied to remove excess aluminum. However, the etching rate of copper
using this method is too slow. Confronting these challenges requires three things:
finding a method of deposition, patterning the metal, and finding a suitable barrier
material that prevents copper from diffusing into SiO2 and Si.1.5
Several metal deposition techniques have been explored, such as electroplating,
physical vapor deposition (PVD), and chemical vapor deposition (CVD). Electroplating
is a two-step method. It requires a seed layer deposition preceding the plating fill step to
insure a low-resistance conductor for the plating current and to assist in the film
nucleation.
In PVD, atoms or small groups of atoms are produced by the evaporation of a
solid or molten source. These atoms are then carried in a low pressure gas phase, and
deposited on the wafers. Uniformity and step coverage are issues in PVD. Conformal
coverage can be defined as the degree to which the film covers both vertical and
horizontal surfaces. The nature of the PVD method causes this problem (i.e. poor
conformal coverage). For example, there are fewer gas-phase collisions between the
source and the wafer and almost no surface reactions. Thus, the species can get in
perpendicular to the wafer from the source and stay where they arrive without desorption
and redeposition.1.7, 1.8, 1.9
Among the above metal fill methods, CVD has important advantages that can be
useful in sub-0.25 :m devices. While PVD delivers atoms or small groups of atoms to
the substrate surface, CVD carries molecules. These molecules can adsorb/desorb or
diffuse on the evolving film many times before they decompose and further film growth.

Consequently, more uniform films are formed and conformal coverage is more likely
with CVD (see Fig.1.1).1.9

Thin Film

Substrate

Substrate

CVD

PVD

Fig. 1.1 PVD (right) Has Limited Conformal

Coverage Compared To CVD (left)
Patterning copper is another challenge in copper metallization. An alternative to
the plasma etching that is available for aluminum metallization is the damascene
process. In this process an insulator (SiO2) is dry-etched to form trenches conforming to
the desired wiring pattern. The trenches are then plugged with copper. Then application
of chemical-mechanical polishing (CMP) of copper down to the insulator surface yields
copper interconnects surrounded by the insulator. The damascene process forms
interconnect and achieves planarization of an interlayer immediately. Once lower-level
planarization is accomplished, the upper-level interlayer and interconnections are easily
formed by repeating the damascene process (Fig.1.2).1.10

T iN
o x id e

o x id e

Cu CVD

Cu

Cu

P o lis h
o x id e

o x id e

Fig. 1.2 Schematic Diagram Of

A Damascene Process1.3
To avoid the copper oxidation and diffusion, the side walls and the bottom surface
of copper interconnects are covered by a diffusion barrier/adhesion layer. For example
TiN is used effectively to prevent diffusion of copper into the surrounding insulator.
1.4 CVD
In chemical vapor deposition, a solid is deposited from the vapor phase via a
chemical reaction that occurs on a substrate surface. CVD can be established and
maintained by different means, for example, heat (thermal CVD), photons (such as laserassisted CVD), electrons, ions or in a plasma (plasma-assisted CVD). CVD processes
are characterized by the heterogeneous decomposition of a reactant on an activated
surface. The overall process (Fig.1.3) may be divided into several primary steps:
adsorption of reactants onto the heated surface, decomposition of the reactant to metal,
and desorption of the reaction by-products.
The steps that take place in a CVD process are illustrated in (Fig. 1.3).1.10
6

Precursor

H2

byproduct

Substrate

Fig. 1.3 CVD Process Steps

a) Transport and absorption of reactants.
b) reaction on the surface to produce the film (circles).
c) desorption of volatile products.

1.5 Precursors For Cu-CVD

For CVD to be generally applicable to IC fabrication, volatile precursors with
adequate stability must be designed and optimized. When choosing CVD precursors
many aspects must be considered. First, the preferred precursors should have high
enough vapor pressure to guarantee easy transportation to the reactor. Second, the
decomposition temperature has to be lower than the substrate temperature. Finally, there
must be no contamination by carbon, fluorine, oxygen and other elements during the
deposition of the copper film.1.11
A number of copper precursors are available and many of them have been used
successfully in the deposition of pure copper films. In general, they can be divided into
two groups, based on the Cu(II) oxidation state, such as Cu(hfac)2, and the Cu(I)

oxidation state, such as Cu(hfac)(vtms) (vtms = vinyltrimethylsilane) (Fig. 1.4). Table

1.1 illustrates some features of Cu(hfac)2 and Cu(hfac)(vtms) as Cu-CVD precursors.1.12

F 3C
O
Cu
O

SiMe3

F 3C

Fig. 1.4 Structure Of Cu(hfac)(tmvs)

Table 1.1 Features Of Representative Copper Precursors1.12
Features

Cu(hfac)2

Cu(hfac)(vtms)

From

solid

liquid

Decomposition

at > 200 C

at > 40 C

Vapor pressure

10 torr at 100C

0.3 torr at 40 C

Reducing agent

required

not required

disadvantages

low deposition rate

decomposes before reaching the substrate

In general Cu(II) precursors require a reducing agent for deposition (Eq. (1.2))
while Cu(I) precursors can deposit pure copper films without the use of a reducing agent
(eq. (1.3)).1.12
Cu(hfac)2 + H2
2(hfac)Cu(L)

Cu(s) + 2 Hhfac
Cu(s) + Cu(hfac)2(g) + 2L (g)

Although Cu(I) precursors produce Cu(s) film via a disproportionation

mechanism (eq.1.3), they can also be reduced to Cu(0) using a reducing agent such as
H2.1.13

1.2
1.3

The most studied Cu(II) precursors for Cu-CVD are Cu(II) $-diketonates, and Fig. 1.5
shows some representative examples.

R'

R = R' = CH3
R = CH3
R' = CF3
R = R' = CF3
R = C(CH3)3 R' = n-C3F7

O
Cu
O

acac
tfac
hfac
fod

R'

Fig. 1.5 The Structure Of Cu(II) $-diketonates

The fluorinated chelates are more volatile than Cu(acac)2. The reason for this
volatility is that the fluorine substitution in the ligand decreases the van der Waals
attractive forces between the molecules.1.11
1.6 Cu(hfac)2-Alcohol Adducts As Precursors
Lai and Griffin conducted a kinetic study of Cu(hfac)2 using hydrogen as a
reducing agent.1.14 From this study they suggested that the rate-limiting step is the
regeneration of hfacH (Eq.1.4).
hfac(ads) + H(ads)

hfacH(g)

1.4

A noticeable improvement in the growth rate under lower CVD temperature was
obtained when water vapor was used as co-reactant in Cu-CVD from Cu(hfac)2 under
H2.1.15 Lecohier et al.1.16 showed that when water was used in combination with
Cu(hfac)2 as precursor for Cu-CVD, the deposition rate increased with the amount of
added water vapor. Cho added alcohols such as isopropyl alcohol, methanol, and
isobutyl alcohol as co-reactants with Cu(hfac)2 and H2.1.17 This study demonstrated that
9

these additives lowered the reduction temperatures and increased the growth rates.
It seems that these protic co-reactants participate in the CVD reaction by
transferring a proton from the additive (R= H or alkyl group) to hfac as illustrated in the
following equations:1.18
ROH

hfac(ads) + ROH

RO(ads) + H(ads)

1.5

RO(ads) + hfacH(g)

1.6

Since the adsorbed hfac displays some anionic character, eq. 1.6 is basically an
acid-base reaction.
Kaloyeros conducted a study to investigate the role of alcohols (EtOH, i-PrOH,
and s-BuOH) in plasma CVD reactions. This study showed that these alcohols supplied
atomic hydrogen. This contribution facilitates the Cu(hfac)2 reduction and leads to
greater hydrogen-precursor interaction and, thus, higher copper growth rate.1.19
In our laboratory Cu(hfac)2(alcohol) adducts have been investigated as precursors
for Cu-CVD. The capacity of these alcohols to act as reducing agents as well as their
ability to transfer a proton makes them good candidates. Furthermore, alcohol adducts
with low melting points, such as Cu(hfac)2(i-PrOH) (m.p 50-53 oC),1.20 may be easier to
introduce into a CVD reactor.
The study of a series Cu(hfac)2(ROH), where ROH = C1, C2, C3, and C4
alcohols, showed that some of the alcohols can improve the copper deposition rate.
Cu(hfac)2(i-PrOH) was found to be the most practical precursor for Cu-CVD.
The growth rate using this precursor was 1.3 0.5 :m/hr under nitrogen as the carrier

10

gas, which is about three times greater than Cu(hfac)2 with hydrogen as the carrier gas
under the same conditions. On the other hand, this study showed that an excess of
alcohol vapor is needed during the CVD run in order to keep the adduct stable.1.20
1.7 Cu(hfac)2(amine) Adducts As Precursors
The Lewis acidity of Cu(II) in Cu(II) $-diketonates stems from the presence of
fluorinated $-diketonate ligands which are strongly electron withdrawing, lowering
electron density on the metal. For example, Cu(acac)2(pyridine) is unstable and loses the
pyridine ligand readily when exposed to air. Cu(hfac)2(pyridine), on the other hand, is
stable in air.1.21
Replacing the alcohols with amines seems to be more appealing since amines are
more basic, which results in more stable adducts with Cu(hfac)2. Accordingly, excess of
amine vapor is not expected to be necessary during the CVD. Furthermore, these
amines, like alcohols, can act as reducing agents. Chapter 2 addresses the synthesis and
characterization of amine adducts of the structure Cu(hfac)2(amine) that could be used as
Cu-CVD precursors. The efficiency of these adducts in Cu-CVD are judged by the film
resistivity and the rate of deposition under hydrogen as the carrier gas. To test the ability
of these amine adducts to act as self-reducing agents, the Cu-CVD experiments were
repeated utilizing the inert gas nitrogen as the carrier gas. In synthesizing
Cu(hfac)2(amine) adducts, many side reactions took place. Chapter 3 of this dissertation
lists the reactions between Cu(hfac)2 and various amines that yielded unusual structures.

11

1.8 Tetrameric Copper(I)-Amide Clusters

Photochemical vapor deposition1.22 is one of the aspects that has been studied in
our group. In this type of copper thin film deposition, the reactant molecules are
electronically excited and these activated molecules may lead to faster film deposition.
In our laboratory, we found that some tetrameric copper(I) amide clusters are
photoactive and that they are potentially good Cu-CVD precursors.1.23 Therefore, we
have been synthesizing and studying a series of these clusters to examine their
potentiality as good sources for copper deposition. The study of tetrameric copper (I)
amides and their photo behavior is given in Chapter 4.
1.9 References
1.1) Pierson, H.O. Handbook of Chemical Vapor Deposition: Principles, Technology
and Applications; Noyes Publications: New Jersey, 1992.
1.2) Jain, A.; Chi, K.; Shin, H.; Farkas, J.; Kodas, T. T.; Hampden-Smith, M. J,
Semiconductor International, 1993, June, 128-131.
1.3) Li, J.; Seidel, T. E.; Mayer, J. W. MRS Bulletin, 1994, August, 15-18.
1.4) Misawa, N.; Ohba, T.; Yagi, H., MRS Bulletin, 1994, August, 63-67.
1.5) Andricacos, P. C., The Electrochemical Society Interface, 1999, 8, 32-37.
1.6) Ho, P. S.; Proc. IX IVC-VICCS, Madrid, 1983, 138-144.
1.7) Arita, Y.; Awaya, N.; Ohno, K.; Sato, M., MRS Bulletin, 1994, August, 68-74.
1.8) Jackson, R. L.; Broadbent, E.; Cacouris, T.; Harrus, A.; Biberger, M.; Patton, E.;
Walsh, T., Solid State Technology,1998, March, 49-56. Plummer; J. D., Deal; M.,
Griffen; P. B., In: Silicon VLSI Technology Fundamentals, Practice and Modeling;
Prentice Hall, Inc, Upper Saddle River,, 2000, Chp. 11.
1.9) Kim, D. H.; Wentorf, R. H.; Gill, W. N., J. Electrochem. Soc., 1993, 140,
3267-3272.

12

1.10) Carlson, J., Acta Chem. Scand., 1991, 45, 864-869.

1.11) Griffin, G. L.; Maverick, A. W. In The Chemistry of Metal CVD. Kodas, T.;
Hampden-Smith, M. eds. New York: VCH. Publishers, Inc. 1994, Chap. 4.
1.12) Gelatos, A.V.; Jain, A.; Marsh, R.; Mogab, C. J., MRS Bulletin, 1994, August,
49-54.
1.13) Kumar, R; Fronczek, F. R.; Maverick, A. W.; Lai, W. G.; Griffin, G. L. Chem.
Mater., 1992, 4, 577-582.
1.14) Lai, W. G.; Xie, Y.; Griffin, G. L. J. Electrochem. Soc., 1991, 138, 3499-3504.
1.15) Awaya, N.; Arita, Y., Jpn. J. Appl. Phys., 1993, 32(9A), 3915-3919.
1.16) Lecohier, B.; Philippoz, J. M.; Calpini, B.; Stumm, T.; van den Bergh, H., J.
Phys. IV C2, 1991, 1, 279-286. Lecohier, B.; Calpini, B.; Philippoz, J. M.;
Stumm, T.; van den Bergh, H., Appl. Phys. Lett., 1992, 60, 3114-3116.
1.17) Cho, C. C., Tungsten and other Advanced Metals for ULSI Applications, MRS,
Pittsburgh, PA,1991, 18-23.
1.18) Doppelt, P.; Baum, T. H., MRS Bulletin, 1994, August, 41-47.
1.19) Kalyeros, A. E.; Zheng, B.; Lou, I.; Lau, J.; Hellgeth, J. W., Thin Solid Films,
1995,262,20-30.
1.20) Fan, H., Ph.D. Dissertation, Louisiana State University, 2000.
1.21) Wolf, W. R.; Sievers, R. E.; Brown, G. H., Inorg. Chem., 1972, 66, 346-348.
1.22) Jones; C. R., Houle; F. A., Kovac; C. A. Baum; T. H. Appl. Phys. Lett. 1985, 46,
p. 97.
1.23) James, A. M., Ph.D. Dissertation, Louisiana State University, 1999.

13

Chapter 2
Cu(hfac)2 Adducts With Amines
2.1 Introduction
As stated in Chapter 1, the use of Cu(hfac)2 alcohol adducts as Cu-CVD
precursors improved the thickness and purity of Cu films.2.1 However, alcohol adducts
need an excess of alcohol vapor for efficient Cu deposition. Therefore, the conversion
of the alcohol precursors to the use of amine adducts seems to be the next logical
choice. In this chapter, the preparation of several Cu(hfac)2(amine) adducts is described
as well as their use as Cu-CVD precursors.
With their greater basicity, amines offer greater stability for the Cu(hfac)2
adducts. This was verified in the studies by Drago and coworkers. For example, the
measured binding constant K2.1 (see equation 2.1) in CCl4 is 1.7 103 for
L = CH3C(O)N(CH3)2 which binds through oxygen vs.107 for L = methylamine which
binds through the nitrogen.2.2
Cu(hfac)2

Cu(hfac)2L

2.1

This is an advantageous feature for CVD since an excess of amine vapor may not be
necessary during the CVD reaction. Primary and secondary amines can be oxidized to
imines; thus, amines can also be reducing agents. An added virtue of using amine
adducts is that amines are potentially capable of transferring a proton to the hfac ligand
during CVD. Pinkas et al.2.3 suggested that the proton transfer from the coordinated
water in Cu(hfac)2(H2O) to the hfac ligand proceeds via the following equation (2.2):

14

H
F 3C

H
O

CF3

F 3C

CF3
O

Cu

Cu
O

CF3

2.2

F3 C

HO

OH

F3C

CF3

Hhfac

To examine their postulate, they used ammonia (NH3) as the protonating agent. The
CVD experiments of Cu(hfac)2 were run under NH3 as the carrier gas. Table. 2.1
summarizes the findings of this study.
Table 2.1 CVD Of Cu(hfac)2 With NH3 As The Carrier Gas
Precursor

Substrate Temperature C

Species Found in the Film

Cu(hfac)2

400

Cu3N, Cu(hfac)2ANH3, CF3COOH, other species:

products of Hhfac reactions with NH3.

Cu(hfac)2

450

Cu+2 is reduced to Cu+1, N, Cu3N,

and metallic copper.

The authors concluded that a proton from NH3 has transferred to the hfac
ligands, which assists in ligand release. They suggested that the dissociation of the
hfac ligand took place in a way analogous to reaction 2.2.2.3
Most of the Cu(II) $-diketonate compounds that were studied for CVD have
square planar geometry. Cu(hfac)2 adducts with one additional ligand are usually
square pyramidal, with basal and apical metal ligand distance of ca. 1.90 and 2.2 D,
respectively. The copper atom is typically displaced 0.15-0.25 D out of the basal plane
toward the apical ligand.2.4

15

The amine adducts that were examined in this work are

Cu(hfac)2(dimethylamine), Cu(hfac)2(isopropylamine), Cu(hfac)2(allylamine)2 ,
Cu(hfac)2(pyrrolidine), and Cu(hfac)2(piperidine) as shown in Fig. 2.1.

CF3
CF3

O
O

CF3

F3C

O
F3C
H3C

H3 C

O Cu
O

NH
H3C

CF3
O

O Cu
CH

NH2

O
CF3

H3C
CF3

b
H2N

F3C

CF3

O
Cu

H2N

F3C

CF3

CF3

CF3
O

CF3
O

F3C

F3C

O Cu

NH

CF3
O

O Cu

NH

O
CF3

CF3

Fig. 2.1 Precursors For Copper CVD

a) Cu(hfac)2(dimethylamine), b) Cu(hfac)2(isopropylamine),
c) Cu(hfac)2(allylamine)2 , d) Cu(hfac)2(pyrrolidine),
e) Cu(hfac)2(piperidine).

16

Our choice for the above amines was mostly based on thermodynamic grounds
(see section 2.5). In our laboratory we attempted to synthesize a series of amine
adducts. However, we found that some of the amine adducts were very difficult to
isolate. The difficulties with these syntheses, and the side products that resulted in
some cases, are described in Chapter 3. The amines that we used successfully, as
described in this chapter, include several whose thermochemistry is well
understood.2.5, 2.6
Equations (2.3-2.8) illustrate the hypothetical reactions of some of theses
precursors under hydrogen and nitrogen as the carrier gases. For purpose of
comparison, Cu(hfac)2(i-PrOH) is included.
(a) Possible reactions under hydrogen:
Cu(hfac)2(i-PrOH) + H2

Cu(hfac)2(i-PrNH2) + H2

Cu(s) + 2Hhfac (g) + i-PrNH2(g)

2.4

Cu(hfac)2(pyrrolidine) + H2 Cu(s) + 2Hhfac (g) + pyrrolidine

2.5

Cu(s) + 2Hhfac (g) + i-PrOH(g)

2.3

(b) Possible reactions under nitrogen:

Cu(hfac)2(i-PrOH)

Cu(s) + 2Hhfac (g) + (CH3)2C=O (g)

2.6

Cu(hfac)2(i-PrNH2) Cu(s) + 2Hhfac (g) + (CH3)2C=NH (g)

2.7

Cu(hfac)2(pyrrolidine) Cu(s) + 2Hhfac (g) + pyrroline

2.8

2.2 Experimental
2.2.1 Synthesis
Syntheses were performed under inert atmosphere in an Ar-filled glove box.
Amines were obtained from Aldrich; pure liquid amines were purged with N2 and stored

17

in the glove box, while dimethylamine was obtained as a deoxygenated solution in

THF. Anhydrous Cu(hfac)2, a blue-gray powder, was prepared according to the
literature 2.7 by dehydrating Cu(hfac)2(H2O) (Strem or Gelest, Inc.) in a desiccator at
reduced pressure over P2O5. The initial products were generally suitable for use as
CVD precursors. Crystals for X-ray analysis were grown by evaporation from solutions
in CH2Cl2 (precursors (b), (c) and (e) in Fig 2.1) or hexanes (precursors (a) and (d) in
Fig. 2.1). Analytical samples were first purified by sublimation or recrystallization.
2.2.1.1 General Procedure
Anhydrous Cu(hfac)2 was dissolved in CH2Cl2 and the stoichiometric amount of
amine added via syringe. Addition of the amine caused an immediate color change
from blue-gray to green. The resulting solution was allowed to stir overnight, and then
the solvent was evaporated, giving the products listed below.
2.2.2 Cu(hfac)2(dimethylamine)
Cu(hfac)2 (4.5 g, 9.4 mmole) was dissolved in 100 mL of dichloromethane and
dimethylamine (4.5 mL of 2 M solution in THF, 9.0 mmole) was added. The solution
was stirred overnight. Evaporation of the solvent left a bright green solid, (3.8 g, 80%)
with melting point of 70-71 C.
2.2.3 Cu(hfac)2 (pyrrolidine)
Cu(hfac)2 (1.0 g, 2.1 mmole) was dissolved in 100 mL of dichloromethane and
pyrrolidine (0.20 mL, 2.4 mmole) was added via a syringe. The solution was stirred
overnight, and then the solvent was evaporated which resulted in an emerald green
solid, (0.98 g, 85%) with melting point of 88-90 C.

18

2.2.4 Other Amine Adducts

The other amines in this study were prepared following the same procedure
described above, except for Cu(hfac)2(allylamine)2, where a 1:2 reactant ratio was
used.2.8
2.2.5 Characterization
All the amine adducts that are reported in this study sublimed readily under
reduced pressure at temperatures 10-20 C below their melting points. Melting points
of sublimed materials were unchanged, confirming that the precursors sublimed intact.
The structures of the amine adducts were concluded from elemental and X-ray analysis.
Table 2.2 summarizes the elemental analysis results.
Table 2.2 Elemental Analysis Of Cu(hfac)2(amine) Adducts
Compound

% Calculated
%C
%H

%N

%C

%Found
%H

%N

Cu(hfac)2 (dimethylamine)

27.57

1.74

2.67

27.83

1.65

2.67

Cu(hfac)2 (pyrrolidine)

30.64

2.02

2.55

30.86

2.16

2.54

Crystals of Cu(hfac)2 (amine) adducts submitted for X-ray analysis were

obtained by slow evaporation from hexane solution in air. Diffraction data were
collected on an Enraf-Nonius CAD4 diffractometer fitted with MoK" source and
graphite monochromator, using the 2-22 scan method. Data were collected at low
temperature (100-180 K), in order to minimize difficulties with disorder in the CF3
groups. Final unit cell constants were determined from the orientations of twenty-five
centered high-angle reflections. The intensities were corrected for absorption using R
scan data for five reflections. Additional crystallographic data, and further data

19

collection and refinement parameters, are summarized in Appendix 1. Fig. 2.2 and Fig.
2.3 ( ORTEP) represent the crystal structures of the amine adducts found in this study.
Crystal data for Cu(hfac)2(pyrrolidine) and Cu(hfac)2(dimethylamine) are summarized
in Table 2.3. The other three adducts were also characterized by elemental and X-ray
analysis: Cu(hfac)2(isopropylamine), Cu(hfac)2(piperidine), and
Cu(hfac)2(allylamine)2.2.8

Fig 2.2 ORTEP Drawing Of Cu(hfac)2(dimethylamine)

20

Fig. 2.3 ORTEP Drawing Of Cu(hfac)2 (pyrrolidine)

21

Table 2.3 Crystal Data And Collection Parameters For Cu(hfac)2(pyrrolidine)

And Cu(hfac)2(dimethylamine)
Cu(hfac)2(pyrrolidine)

Cu(hfac)2(Me2NH)

Formula

C14H11CuF12NO4

C12H8CuF12NO4

Formula weight

548.77

521.73

a/

9.0201(13)

10.6865(10)

b/

9.8876(9)

8.9631(8)

c/

11.4485(6)

19.6703(15)

"//

66.872(7)

90

$//

83.297(11)

100.674(7)

(//

87.452(12)

90

V/3

932.6(2)

1851.5(3)

Dcalc/g cm3

1.954

1.872

Space group

P1%, No. 2

P21/n

T/K

100(1)

293(2)

:/mm1

1.309

1.316

R(F) (all data)

0.032

0.0735

Rw(F2) (all data)

0.038

0.1716

2.2.6 CVD Reactions

CVD experiments were carried out in a vertical cold wall CVD assembly under
atmospheric pressure.2.9 The carrier gases used were either hydrogen or nitrogen with a
flow rate of 400 mL/min established and observed throughout the experiment by a flow
meter. The substrates were borosilicate glass disks adhered to a metal susceptor with
silver paint (SPI). The metal susceptor was heated electrically to the required
temperature for Cu deposition. The evaporator flask was placed in an oil or sand bath
and heated to near the precursor melting point. When the evaporator and the substrate
22

had reached the targeted temperatures, and the carrier gas flow was established, the
precursor was then introduced into the reactor and the CVD experiment was run for one
hour. A flow of the carrier gas was run into the reactor ca. 20 min afterwards while the
substrate was allowed to cool to room temperature.
The thickness and resistivities of the films were determined for at least five
samples for each precursor. The films thicknesses were measured by a stylus
profilometer while resistivities were evaluated with a four-point probe. Both
measurements were taken at the same positions (in the center and on four sides) for
every sample (Fig. 2.5).

Cut on the film

The position where resistivity was measured

The position where thickness was measured

Fig. 2.4 Depiction Of Cu-CVD Film Measurement

The four-point probe reading indicates the resistance (R). This reading was converted to
bulk resistivity (Draw ) as given in equation 2.9.
Draw = C.F.TR

2.9

where T= film thickness and C.F.= correction factor. The correction factor for our

23

probe and substrate size is 3.9273.2.10 To correct for the systematic error caused by the
four-point probe machine, equation 2.10 was applied.
Dfilm = (1.67 :S cm Draw)/DCu

2.10

Where DCu=1.16 :S cm, the apparent resistivity of Cu foil, (0.0125 nm thick and 99.9%
pure) obtained from the same four-point probe machine.2.1
Table 2.4 represents an example of the measurements of the thickness and resistivity of
a single sample.
Table. 2.4 Film Thickness And Resistivity Of One Cu Film Deposited
From Cu(hfac)2(dimethylamine) Under Hydrogen
Position of
Mesurments

Thickness
(nm)

Sheet Resistance
(mS/sq)

Bulk Resistivity
(:S.cm)

450

0.00393

2.35

500

0.00359

2.14

715

0.00263

1.57

675

0.00774

4.67

645

0.00174

1.00

Average

600 110

0.0038 0.0024

2.3 1.4

2.3 Results And Discussion

2.3.1 Thermodynamic Considerations
The availability of thermodynamic data for alcohols made it easy for our group
to predict which alcohol will serve best for CVD. For example, the enthalpy for
dehydrogenantion of methanol to formaldehyde is 85.1 kJ/mol while the enthalpy for
dehydrogenation of 2-propanol to acetone is 54.3 kJ/mol. Therefore, we predicted that
the latter alcohol will be more favorable as a reducing agent for Cu(hfac)2. The

24

experimental work that was conducted on a series of alcohols showed that the behavior
of these corresponding alcohol adducts is generally consistent with the alcohol
enthalpies of dehydrogenation. 2.1
The thermodynamic data that are available for amines are not as well
established. This stems from the fact that their oxidized counterparts are typically
unstable and difficult to isolate. Enthalpies of dehydrogenation of some amines are
summarized in table 2.3.
Table 2.5 Enthalpies Of Dehydrogenation
Of Some Amines
Amine

)H ( KJ/mol)

methylamine

92 calculated 1

ethylamine

71 calculated 1

dimethylamine

64 calculated 1

piperidine

87 experimental 2

pyrrolidine
1 Ref. 2.5
2
Ref. 2.6

67 experimental 2

The dehydrogenation of several 5- and 6-carbon secondary amines to the

corresponding imines were reported in the literature to be endothermic by 80-96
kJ/mol.2.11 Therefore, we predicted that dimethylamine and pyrrolidine might give
self-reducing CVD precursors. We also used i-PrNH2, because it should be relatively
easy to dehydrogenate (in analogy with i-PrOH). Finally, we chose allylamine because
its dehydrogenation reaction may be more favorable due to the added stability
contributed from the conjugation in the imine.

25

2.3.2 Synthesis And Properties

The adducts described here were prepared in DCM solutions by direct reaction
of anhydrous Cu(hfac)2 with the stoichiometric amount of amine.
Using Cu(hfac)2(H2O) as starting material, or carrying out the reaction in air, led to
color change indicating adduct formation, however, products obtained in this manner
were frequently oils or mixture. In addition, although the Cu(hfac)2 solutions changed
color from blue to green immediately on addition of the amines, attempts to isolate the
adducts after a short reaction times often led to oily mixtures. A minimum of several
hours of stirring was required for the adduct formation. Furthermore, except for
allylamine, the reaction of Cu(hfac)2 with amines in DCM using the ratio 1:2 did not
produce isolable Cu(hfac)2(amine)2 adducts. Instead, oils were obtained.
The objective of this study is to prepare amine adducts Cu(hfac)2(L) (L=amine)
for use in Cu-CVD. Several amine adducts were successfully synthesized and
characterized (see Table 2.4). All adducts with the exception of Cu(hfac)2(allylamine)2
adduct displayed square pyramidal geometry with the hfac ligand twisting out of the
plane, allowing one of the Cu--O bonds to take the apical position. Thus, three O and
one N ligand are in the equatorial plane (with Cu-O and Cu-N distances of 1.95-1.99 D),
and one O atom from a hfac ligand is in the apical position (Cu-O 2.22-2.25 D).
All of the amine adducts that are reported here were volatile and sublimed
readily under reduced pressure. The melting points of sublimed adducts were checked
as evidence that they sublimed intact.
This contrasts with the behavior of the adducts with water and alcohols, which

26

can dissociate under vacuum or in a stream of the carrier gas.

2.3.3 CVD Results
2.3.3.1 Cu(hfac)2(H2O)
For comparison, Cu(hfac)2(H2O) was used as a precursor for CVD experiments.
The results of this deposition under hydrogen are given in Table 2.5 No films were
obtained when nitrogen was used as the carrier gas.
2.3.3.2 Amine Adducts
Cu-CVD experiments with the amine adducts were conducted under hydrogen to
examine their efficiency as precursors. Table 2.5 summarizes the results of the CuCVD of Cu(hfac)2(amine) adducts using hydrogen as the carrier gas.
CVD experiments under the carrier gas H2 were initially attempted at lower
substrate temperatures. The resulting films were very thin and transparent. Deposition
improved at higher substrate temperatures. Thus, the substrate temperature was
gradually raised until the maximum deposition rate was achieved. For example, for
each amine adduct, the CVD experiment was run at lower substrate temperature for an
hour. Then the same run was repeated at 10 C substrate temperature higher. Raising
the substrate temperatures was continued till a maximum film was formed.
Cu(hfac)2(amine) adducts were compared to the alcohol adducts in terms of the
film thickness and resistivities.2.1 Except for Cu(hfac)2(allylamine)2, the results in Table
2.4 indicate that these amine adducts do not show improvement regarding the qualities
of the deposited films.

27

Table 2.6 CVD Results Under H2

Substrate
Temp.(oC)

Resistivity
(:S*cm)

Thickness
(nm)

Dep.
Rate
(nm/min)

m.poC

Cu(hfac)2(H2O)

220

3.5 0.7

1000 400

16 3

125-128

Cu(hfac)2(pyrrolidine)

225

3.5 0.7

500 200

8 3

88-90

Cu(hfac)2(piperidine)(2.8)

230

4.8 0.3

280 70

5 1

82-83

Cu(hfac)2(allylamine)2 (2.8)

230

2.60.9

1000 300

20 7

128-130

Cu(hfac)2(isopropylamine)(2.8)

265

5.10.9

500 200

10 4

90-91

Cu(hfac)2(dimethylamine)

285

3.4 0.9

780 190

16 4

70-71

Precursor

The amines precursors were also studied under nitrogen as a carrier gas to
determine their behavior as self-reducing precursors (see Table 2.5).
Table 2.7 CVD Results Under N2
Substrate
Temp. (C)

Resistivity
(:S*cm)

Thickness
(nm)

Dep. Rate
(nm/min)

Cu(hfac)2(piperidine)*

290

4050

4300

72

Cu(hfac)2(pyrrolidine)*

285

200

1000

17

Cu(hfac)2(allylamine)2

275

19,00012,000

1900600

4010

Cu(hfac)2(isopropylamine)

285

109

30001000

5020

Precursor

* Only one film was thick enough to be characterized.

The Cu-CVD that utilized Cu(hfac)2(amine) precursors under N2 confirmed that
these adducts can act as self-reducing precursors. Most of the films that were
deposited under N2 were too thin to be characterized. However, one sample each
prepared from Cu(hfac)2(piperidine) and Cu(hfac)2(pyrrolidine) were thick enough to
be measured (see Table 2.7).
In order to determine the deposition chemistry of Cu(hfac)2(pyrrolidine) under
N2, the organic byproducts were analyzed by GC/MS.2.8

28

Pyrrolidine oxidized to the corresponding imine as in equations (2.11).2.6

+ H2
N
H

2.11

These fragments were not seen for the CVD under H2. This led us to conclude that
under N2, pyrrolidine oxidized to its imine counterpart, whereas H2 acts as the principal
reductant when it is present.
2.3.4 Discussion
In this work we have been studying a series of Cu(hfac)2(amine) adducts as CuCVD precursors. We found that the amine ligands do not dissociate in the vapor phase;
this means that they are much more stable than those of alcohols. To compare their
efficiency to other precursors, CVD experiments were conducted under H2. The
results we obtained indicate that some of these adducts show improvements in terms of
deposition rate, such as Cu(hfac)2(allylamine)2. Actually, we found that deposition rate
improves with elevated substrate temperatures. For example, Cu-CVD using
Cu(hfac)2(dimethylamine) under hydrogen, using a substrate temperature of 261 C,
yielded a deposition rate of 4.8 nm/min, vs. 16 nm/min at 285 C (Table 2.6).
However, intrinsic instrumental problems make it difficult for us to consistently
reproduce experiments at substrate temperatures $ 300 C. The amine adducts in the
study all appear to be self-reducing CVD precursors, depositing very thin Cu films
under N2 CVD. In order to deposit thicker Cu films under nitrogen, higher substrate

29

temperatures may be needed, which are beyond the range of our CVD reactor. The
lower resistivity of the Cu film obtained with Cu(hfac)2(pyrrolidine) under N2 reflects a
higher purity film compared to Cu(hfac)2(piperidine). This can be explained as follows:
pyrrolidine is easier to oxidize to the corresponding imine than piperidine. Wiberg et
al.2.6 showed that the reaction in equation 2.11 is more favorable toward having the
double bond in the five- member ring by 20.5 kJ / mol.
2.3.5 Film Quality
The quality of a single sample can be deduced from the standard deviation of
the average value of the five measurements. For example, the high value of the
standard deviation for the measurements of thickness in Table 2.4 reflects that the
surface of this film is rough. This roughness affects the resistivity of the film as well.
As the roughness increases the calculated resistivity of the sample also increases,
lowering the apparent quality of the film. We found that the quality of the films
obtained under hydrogen as the carrier gas is better than those deposited
under nitrogen. This may indicate that hydrogen is still needed for assisting the
reduction of Cu(II) to the metal and transferring protons to the hfac .
2.3.6 Adhesion Measurement
To test the adhesion of the copper deposited films to the substrate glass, we
conducted the Scotch tape test.2.12 This test was conducted on the same samples that
were characterized in table 2.4. In this test the thin film was cut via a razor blade along
the horizontal and vertical planes.

30

The results of this test are summarized in table 2.7. The percentage of the film adhered
to the surface was estimated according to the literature.2.12
Table. 2.8 Adhesion Test Results
Compound

Percentage (%) of film adhered to the substrate

surface (average of 5 films)

Cu(hfac)2(H2O)

20 10

Cu(hfac)2(pyrrolidine)

20 10

Cu(hfac)2(piperidine)

40 10

Cu(hfac)2(allylamine)2

70 10

Cu(hfac)2(isopropylamine)

30 10

Cu(hfac)2(dimethylamine)

40 10

From the above results summarized in table 2.8 the amine adducts seem to adhere better
to the glass surface than the hydrate adduct. Although glass substrates are not used in
industry, our results may still represent as an improvement when it comes to Cu-CVD.
2.6 Conclusions
The adducts in this study with the exception of Cu(hfac)2(allylamine)2 displayed
square pyramidal geometry. In this configuration the hfac ligand is twisting out of the
plane where one of the Cu--O bonds accommodates an axial position.
The CVD under H2 showed that except for Cu(hfac)2(allylamine)2, these amine
adducts do not display improvement regarding the qualities of the deposited films. The
CVD that utilized Cu(hfac)2(amine) precursors under N2 verified that these adducts are
self-reducing precursors. The roughness of the film's surface increases the calculated
resistivity of the sample, lowering the apparent quality of the film.
We found that the quality of the films obtained under hydrogen as the carrier
gas is better than those acquired under nitrogen. This may indicate that hydrogen is still
31

needed for assisting the reduction of Cu(II) to the metal and transferring protons to
hfac .
Cu films deposited using Cu(hfac)2(amine) adducts adhere somewhat better to
the glass surface than those deposited using Cu(hfac)2(H2O).
2.7 References
2.1) Fan, H. Ph.D. Dissertation, Louisiana State University, 2000.
2.2) McMillin, D. R.; Drago, R. S; Nusz, J. A. J. Am. Chem. Soc.,1976, 98,
3120-3126.
2.3) Pinkas, J.; Huffman, J. C.; Baxter, D. V.; Chisholm, M. H.; Caulton, K. G. Chem.
Mater. 1995, 7, 1589-1596.
2.4) Griffin, G. L.; Maverick, A. W. In The Chemistry of Metal CVD. Kodas, T.;
Hampden-Smith, M. eds. New York: VCH. Publishers, Inc. 1994, Chap. 4.
2.5) Jackman, L. M.; Packham, D. I. Proc. Chem. Soc. 1957, 349-350.
2.6) Wiberg, K. B.; Nakaji, D. Y.; Morgan, L. M., J. Am. Chem. Soc., 1993, 115,
3527.
2.7) Bertrand, J. A.; Kaplan, R. I. Inorg. Chem., 1966, 5, 489-491.
2.8) Cygan, Z. T., unpublished work.
2.9) Kumar, R; Fronczek, F. R.; Maverick, A. W.; Lai, W. G.; Griffin, G. L. Chem.
Mater., 1992, 4, 577-582.
2.10) Tsai, J. C. C., "Diffusion", in Sze, S. M., Eds. VLSI Technology, 2ed, NYC:
McGraw-Hill, 1998; Chap. 7.
2.11) Hfelinger, G.; Steinmann, L. Angew. Chem. Int. Ed. Engl. 1977, 16, 47-48.
2.12) ASTM Test Method D3359-97 (method B), ASTM, West Conshohocken, PA,
1998.

32

Chapter 3
Attempted Synthesis Of Other Cu(hfac)2 Adducts
3.1 Introduction
The goal of my work is to prepare novel Cu-CVD precursors of the structure
Cu(hfac)2L, where L is either alcohol or amine. However, we found that the 1:1
reactions with Cu(hfac)2 and certain amines resulted in compounds with other formulas.
This chapter is dedicated to the synthesis and characterization of the products of
reactions between Cu(hfac)2 and the following ligands: triethylamine, diethylamine,
quinuclidine, diisopropylethylamine and propylene glycol.
3.2 Experimental
For general experimental manipulations see section 2.2.
3.2.1 Reaction Of Cu(hfac)2 With Triethylamine
We attempted to prepare Cu(hfac)2(NEt3) as follows: In the dry box, Cu(hfac)2
(0.474 g, 1 mmole) was dissolved in 50 mL of dichloromethane and triethylamine (0.14
mL, 1 mmole; distilled twice under N2 before use) was added. The solution was stirred
overnight. Evaporation of the solvent resulted in an emerald green oil. The oil was
triturated with hexane in an ice/salt bath. A very small quantity of a lime-green solid
separated with a melting point of 63-65 C. This lime-green solid sublimed under
vacuum at 40 C and its melting point was 68-69 C after sublimation. The
recrystallization of the sublimed solid was performed by dissolving it in chloroform and
layering with cyclohexane. Two types of crystals separated: lime green needles and
emerald green plate like crystals. The lime green crystals are (Et3NH)[Cu(hfac)3].

33

(See structure of the hydrated form of this compound, in section 3.2.2.). The emerald
green crystals were carefully separated and recrystallized using the same method. The
crystals turned out to be [Et3NH][(hfac)2Cu(-OH)Cu(hfac)2]. (Fig. 3.1)

Fig. 3.1 ORTEP Drawing Of [Et3NH][(hfac)2Cu(-OH)Cu(hfac)2]

3.2.2 (Et3NH)[Cu(hfac)3].H2O
To see if we could obtain (Et3NH)[Cu(hfac)3] using a different route, we tried
the following reaction. In this preparation we used the stoichiometric ratio of the
reactants. In the dry box Cu(hfac)2 (2.0 g, 4.2 mmole) was dissolved in 200 mL of
CH2Cl2 and NEt3 (0.60 mL, 4.2 mmole) was added to it and stirred overnight. Hhfac
(0.61 mL, 4.2 mmole) was added to this mixture and left to stir overnight. The
evaporation of the solvent resulted in a bright lime green solid (2.8 g, 83%) with a

34

melting point of 55-58 C. Crystals were obtained by slow evaporation of a

CHCl3/cyclohexane solution in air. These crystals were lime green needles and have
the structure illustrated in (Fig. 3.2). The structure of the anhydrous form of this
compound, (Et3NH)[Cu(hfac)3], obtained in section 3.2.1 was also determined and
found to be similar. (See Table A-3 in Appendix A.)

Fig. 3.2 ORTEP Drawing Of (Et3NH)[Cu(hfac)3].H2O

3.2.3 Reaction Of Cu(hfac)2 With Quinuclidine

Cu(hfac)2 (0.955 g, 2.00 mmole) was dissolved in 50 mL of DCM, and freshly
sublimed quinuclidine (0.222 g, 2.00 mmole) was added. The solution was stirred
overnight, and then the solvent was evaporated resulting in a light green solid (0.942 g,
28 %) with melting point of 84-86C. Crystals were obtained from hexane by the slow
evaporation of the solvent in air. This material did not have the desired

35

Cu(hfac)2(quinuclidine) structure; instead it contained quinuclidinium ions and

hydroxide-bridged trinuclear [Cu3(hfac)6(OH)2]2- anions. (Fig.3.3)

Fig. 3.3 ORTEP Drawing Of The Dianion [Cu3(hfac)6(OH)2]2From The Structure Of (quinuclidinium)2[Cu3(hfac)6(OH)2]
3.2.4 Reaction Of Cu(hfac)2 With Diethylamine
This reaction was performed as follows: In the dry box, Cu(hfac)2
(1 g, 0.002 mole) was dissolved in 50 mL of dichloromethane and diethylamine
(0.21 mL, 0.002 mole; distilled twice under N2 before use), was added. The solution
was stirred overnight. Evaporation of the solvent resulted in a dark green oil. The oil
was triturated with hexane in an ice/salt bath. White and green solids separated. The
green solid was crystallized by slow evaporation of a solution in CHCl3/cyclohexane in
air, producing needle like crystals of [Cu3(hfac)6(OH)2][HNEt2]2. The anion
[Cu3(hfac)6(OH)2]2- in this salt has a structure very similar to that in the quinuclidinium
salt (Fig. 3.3).

36

3.2.5 Reaction Of Cu(hfac)2 With Diisopropylethylamine

This synthesis was conducted as follows: In the dry box, Cu(hfac)2
(2.39 g, 5.00 mmole) was dissolved in 200 mL of dichloromethane and
diisopropylethylamine (0.90 mL, 5.00 mmole; distilled twice under N2 before use), was
added. The solution was stirred overnight. Evaporation of the solvent the following
day resulted in an olive green oil. The oil was taken up in hexane; and the slow
evaporation (in air) of the solvent resulted in dichroic olive plate-like crystals of
trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2. (Fig.3.4)

Fig. 3.4 ORTEP Drawing Of trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2

37

3.2.6 Attempted Synthesis Of Cu(hfac)2(propylene glycol)2

Our group previously conducted this synthesis using a 1:1 ratio of Cu(hfac)2 and
propylene glycol, which resulted in a dark green solid with a melting point of 54-56 oC.
Despite the 1:1 ratio of reactant, the only crystalline product obtained was
Cu(hfac)2(propylene glycol)2.3.1
In this work we tried to synthesize Cu(hfac)2(propylene glycol)2 deliberately by
using a 1:2 ratio of the reactants. Cu(hfac)2 (1 gram, 2.1 mmole) was dissolved in 100
mL of CH2Cl2. To this, propylene glycol (0.31 mL, 4.2 mmole) was added and stirred
overnight. The evaporation of the solvent resulted in an emerald green solid (1.16 g)
melting at 49-51oC.
An attempt to grow crystals of this solid in air produced only Cu(hfac)2H2O.
Thus, we concluded that the adduct is not stable in air and the ligands were displaced.
This synthesis was repeated as above. The resulting solid was crystallized from CH2Cl2
in the dry box. To our surprise the crystal structure of this complex turned out to be a
tetramer of Cu(II), [(hfac)Cu(:3-OCH2CH(OH)CH3)]4, as shown in (fig. 3.5).
3.2.7 X-ray Structure Determinations
X-ray diffraction data were collected using Enraf-Nonius CAD4 or KappaCCD
diffractometers. Crystal data are summarized in table 3.1. For crystal data details see
Appendix A.

38

Fig. 3.5 ORTEP Drawing Of [(hfac)Cu(:3-OCH2CH(OH)CH3)]4

39

40

91.949(3)
99.782(3)
110.015(3)

"//

$//

(//

P21/n

0.1533

Rw(F2) (all data) 0.1517

7= [(hfac)Cu(3-OCH2CH(OH)CH3)]4

3=(Et3NH)[Cu2(hfac)4(-OH)]

4=(quinuclidinium)2[Cu3(hfac)6(OH)2]

6= Cu(hfac)2(CF3COCH(CF3)CHCHN(i-Pr)2)2

0.129

0.090

1.308

100(1)

C2/c (No. 15)

1.913

5609(3)

90

99.758(2)

90

16.594(5)

20.869(6)

16.434(5)

1615.28

C38H32Cu3F36N2O14

2= (Et3NH)[Cu(hfac)3]

0.2794

0.115

1.246

100(1)

P43212 (No. 96)

1.900

5914.3(15)

90

90

90

32.132(5)

13.567(2)

13.567(2)

1691.37

C44H36Cu3F36N2O14

5=Cu3(hfac)6(OH)2](Et2NH2)2

0.181

0.078

1.292

170(1)

P1bar, No. 2

1.886

1892.2(8)

108.929(14)

102.170(14)

93.892(13)

18.353(5)

11.998(3)

9.396(2)

1074.52

C26H21Cu2F24NO9

1= (Et3NH)[Cu(hfac)3].H2O

0.917
0.1046

:/mm

0.886

100(1)

0.0892

T/K

R(F) (all data)

P1bar, No. 2
100(1)

Space group

1.822

2869.0(16)

90

98.383(17)

90

12.896(4)

1.791

Dcalc/g cm3

1492.45(11)

12.8520(5)

c/

V/

11.7170(5)

b/

12.439(4)

10.7570(5)

a/
18.078(6)

786.91

C21H21CuF18NO7 C21H19CuF18NO6

Formula weight 804.93

Formula

Table 3.1 Crystal Data And Collection Parameters

0.126

0.050

0.631

150(1)

P1bar, No. 2

1.645

1122.5(7)

109.655(16)

109.532(19)

95.166(18)

11.253(3)

10.753(4)

10.735(4)

1112.21

C36H36CuF24N2O6

0.163

0.175

1.823

100(1)

P2/c, No. 12

1.831

5015(3)

90

118.793(15)

90

23.767(8)

10.014(3)

24.046(8)

1382.74

C32H32Cu4F24O16

3.3 Results And Discussion

3.3.1 Reactions Of Cu(hfac)2 With Amines
3.3.1.1 Reactions Of Cu(hfac)2 With Triethylamine
We tried to prepare Cu(hfac)2NEt3 according to the literature procedure.3.2
However, we obtained an oil and we were able to isolate only Cu(hfac)3(HNEt3) with
minimal yield. Using the stoichiometric ratio of the reactants to prepare
Cu(hfac)3(HNEt3) gave a good yield of Cu(hfac)3(HNEt3)H2O. The elemental analysis
that was reported in the literature for "Cu(hfac)2NEt3", actually, agrees more with our
composition than with "Cu(hfac)2NEt3". Table 3.2 summarizes the elemental analysis
results.
Table 3.2 Elemental Analysis
Compound

% Calculated
C

% Found
N

Cu(hfac)2NEt3 (1)

33.20

2.96

2.42

32.75

2.78

1.93

Cu(hfac)3(HNEt3)

32.05

2.43

1.78

---

---

---

Cu(hfac)3(HNEt3) H2O(2)

31.34

2.5

1.74

32.88

2.49

1.77

30.45

2.46

1.27

30.22

2.22

1.52

[Cu(hfac)2OHCu(hfac)2]HNEt3(2)
(1) Structure suggested in reference(3.2)
(2) Data obtained from this work.

The percentage of nitrogen found in the literature is 20% less than the calculated
value. Thus, we propose that they did not have Cu(hfac)2NEt3. The values in table 3.1
suggest that they probably had Cu(hfac)3(HNEt3).
Thermodynamic studies of the interaction between Cu(hfac)2 and NEt3 showed
that the observed enthalpy was 3 Kcal/mole lower than expected for reaction 2.1.3.3
They attributed this difference to the steric effect exerted by the bulky ligand, which
41

made the interaction weak. However, we believe this difference is because the reaction
is not a simple adduct formation. In related work, Belford et al.3.4 suggested that the
green crystals that resulted from the reaction of Cu(hfac)2(H2O) with quinuclidine (Q)
in CCl4 might contain Cu(hfac)2(Q) cocrystallized with quinuclidinium hydrochloride:
[Cu(hfac)2(Q)][QH+Cl-].
Based on these findings in the literature and structures presented in this work, it
appears that reactions between Cu(hfac)2 with Lewis bases do not always result in the
simple addition of the base to the acidic Cu(II). The formation of some of these
compounds that resulted from the reactions of Cu(hfac)2 with NEt3, NHEt2, and
quinuclidine can be explained through proton transfer. It is possible that the source of
the proton in this reaction is the presence of a small amount of H2O as follows:
2 Cu(hfac)2 + NEt3

H2 O

Cu(hfac)2 + HNEt3

[(hfac)2 Cu u-OHCu(hfac)2]

Cu(hfac) + (hfac)

+ HNEt 3

+ HNEt3

Cu(hfac)3HNEt3

Cu(hfac)2 + (hfac) HNEt3

3.3.1.2 Structures Of The New Cu(II) Complexes.

Generally, Cu(II) is found in three different geometries: square planar; square
pyramidal with a longer apical Cu-L ligand; and six-coordinate with tetragonally
elongated geometry (four approximately equal equatorial bonds, and two longer bonds
in the ''z'' direction). For example, in (Et3NH)[Cu(hfac)3]"H2O, Cu(II) has a

42

coordination number of six (Fig. 3.1). The equatorial Cu-O bonds are 1.959(2) and
2.075(3) D and the axial Cu-O bonds Cu1-O5 and Cu1-O2 respectively are 2.170(3) and
2.187(2) D. Also the nitrogen atom of the amine is hydrogen-bonded (H-bonded) to O1
of the water molecule, N-O1 2.821(4) D and N-H-O 176. Water O1 is also H-bonded
to O6 and O2 of an adjacent Cu complex. The complex (Et3NH)[Cu(hfac)3] also has six
coordination around Cu(II). The equatorial Cu-O distances are 1.954(2)-2.022(2) D,
and the axial Cu-O distances are Cu1-O6 2.187(2), Cu1-O3 2.335(2) D. The amine
nitrogen N1 is H-bonded to O3 (N1-O3 2.911 D; N-H-O 168).
The compound (Et2NH)[Cu2(hfac)4(:-OH)] (Fig. 3.2) has Cu- -Cu separation of
3.0449(5) D. The equatorial Cu-O distances are 1.934(2)-1.976(2) D and axial Cu-O
distances are: Cu1-O5 2.20, Cu1-O8 2.63, Cu2-O4 2.96, Cu2-O9 2.204(2) D. Both Cu
atoms are displaced slightly out of their equatorial planes toward the closer axial O
atom (O5 and O9).
3.3.1.3 Reaction Of Cu(hfac)2 With Diisopropylethylamine
On the other hand, the structure obtained from treating Cu(hfac)2 with
diisopropylethylamine, trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2, points to
some sort of oxidation taking place. Whether this oxidation took place during the
course of the synthesis reaction or during the crystallization process, was not examined.
If the oxidation occurred during the synthesis, then visible light might be involved in
the initiation of the oxidation. However, if this oxidation took place after the adduct
was exposed to air, then atmospheric oxygen could be what promoted the oxidation of
the amine or it could be photochemical oxidation. This point was not studied further

43

since it is not relevant to chemical vapor deposition.

Amines can be oxidized via photochemical or electrochemical processes. While
the overall oxidation involves two electrons, it is well established in the literature that it
occurs via one electron cation radicals. Scheme I shows the proposed steps in the
anodic oxidation of tripropylamine, Pr3N.3.5

Pr3N

Pr3N + e

Pr3N + Pr3N
Pr2NCHCH2CH3
2Pr2NCHCH2CH3

(3.1)

Pr2NCHCH2CH3 + Pr3NH

(3.2)

Pr2N=CHCH2CH3 + e

(3.3)

Pr3N + Pr2NCH=CHCH3

(3.4)

Pr2N=CHCH2CH3 + H2O

Pr3NH2 + CH3CH2CHO

(3.5)

Pr2NCH=CHCH3 + H2O

Pr2NH + CH3CH2CHO

(3.6)

Scheme (I): The Anodic Oxidation Of A Teriary Amine

The protonated forms of amines are always the major product in the amine
oxidation reactions. It was thought that the amine cation radical is capable of
abstracting a hydrogen atom from the solvent or from water, if present, to give the
protonated amine and the solvent or hydroxyl radicals, from water, that may complicate
the reaction.3.5, 3.6

44

The most likely method of producing the skeleton we find is via oxidation of the
ethyl group in (i-Pr)2NEt, making (i-Pr)2NCH=CH2 (similar to the product of reaction
3.4). This enamine is nucleophilic at the terminal CH2 group (because of the
(i-Pr)2N=CHCH2 resonance structure, which gives the overall compound partial positive
charge at N and partial negative charge at CH2), so it could attack the Hhfac at the
carbonyl carbon atom.
Yufit et al.3.7 made a rather closely related compound. This compound was
prepared from triethylamine and (dibenzoylmethanato)antimony tetrachloride (Fig. 3.6):

NEt2
Ph
O

NEt2

Cl

Ph

Ph
Cl

Cl
Ph

Cl

Fig. 3.6 The Delocalized Structure

Of 2,4-dichloro-1-diethylamino-3,5-diphenyl-1,3-pentadien-5-one.
The authors stated that in their crystal structure, the PhCO group is twisted out
of the plane so that it will fit next to the rest of the molecule, and most of the bond
distances are rather clearly single or double. So they call it a "localized'' structure.
However, the C-N bond (1.34 D) is shorter than a single bond, and the geometry at the
C=C-N group is all coplanar. Therefore, it's a little similar to our highly delocalized
structure. Accordingly, we suggest that
trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2 was produced via the mechanism
shown in scheme II.

45

[O]

R2NCH2CH3

R2NCH2CH3

-H

R2N

CH3

O
H
C

hfacH

NR2
CH

HC

C
C
H

H2
C

C
H2

F3C

CH2

F3C

CH3

CH2

R2N

H
R2N

R2N

R2NCH2CH3

C
H

CF3

-H2O

HO

C
F3C

NR2

C
C
H2

H
C

NR2
C
H

CF3

CF3

Scheme II: Illustration Of The Possible Path For Producing

The Ketoenamine Ligand In
trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2
In the complex trans-(hfac)2Cu(CF3COCH=C(CF3)CH=CHN(i-Pr)2)2, the Cu(II)
center is bound to four hfac O atoms (Cu1-O1, 1.9581(12)D, Cu1-O2 1.9374(12) D) and
two O atoms from the ketoenamine ligands (Cu1-O3, 2.4097(13) D).

46

3.3.2 Cu(hfac)2 And Propylene Glycol

Our group reported Cu(hfac)2(i-PrOH) as the first liquid Cu(II) precursor for Cu
CVD.3.8 Interestingly, this compound exhibited improved deposition rate and required a
lower deposition temperature under nitrogen compared to the water adduct. A
comparison between the performance of Cu(hfac)2(i-PrOH) under hydrogen and
nitrogen is given in table 3.1.3.8
Table 3.3 CVD Results Using Cu(hfac)2(i-PrOH)
Feature

H2

N2

Deposition rate (nm / h)

540 150

1300 500

Minimum deposition temperature (C)

200

160

This compound is a self-reducing precursor, and the collected byproduct under

the inert gas nitrogen is the oxidized form of i-PrOH, acetone, as illustrated in the
following equation:
Cu(hfac)2(i-PrOH)

Cu(0) + 2Hhfac + (CH3)2C=O

3.7

However, i-PrOH dissociates readily from the adduct under the CVD conditions.
Therefore, it was necessary to use excess i-PrOH vapor to stabilize the precursor. The
need for excess i-PrOH vapor during the CVD run made us search for more stable
alcohol adducts to eliminate the use of the excess of alcohol vapor during the CVD run.
Diols and ether-alcohols might offer more stability to the adduct by binding to
the Cu(II) center through their two oxygen atoms. To examine this hypothesis,
James(3.1) has studied a series of diol and ether-alcohol adducts as Cu CVD precursors,
including the adducts of Cu(hfac)2 with ethylene glycol, 2-methoxyethanol, 1-methoxy2-propanol
47

and propylene glycol. In this study, it was found that the additional ligands in these
compounds are often monodentate, that is, only one oxygen of the ligand is coordinated
to the Cu(II) center. All of these compounds deposited copper films under hydrogen
without the use of excess diol or ether-alcohol. Among these precursors,
Cu(hfac)2(propylene glycol) gave the best copper film quality.3.9
My contribution to this work is directed toward the precursor
Cu(hfac)2(propylene glycol). James' s attempts to prepare Cu(hfac)2(propylene glycol)
using a 1:1 ratio of the reactants resulted in a dark green solid with melting point of 5456 C. Although the elemental analysis suggests that the complex is
Cu(hfac)2(propylene glycol), good crystals were not acquired. Actually, the crystals
that were obtained from this reaction were of Cu(hfac)2(propylene glycol)2 with two
propylene glycol ligands mono-coordinating to the Cu(hfac)2. Thus, my goal was to
synthesize this compound, Cu(hfac)2(propylene glycol)2, using different reactant ratios.
In my experiments, the reaction of Cu(hfac)2 with two equivalents of propylene
glycol resulted in the formation of [(hfac)Cu(:3-OCH2CH(OH)CH3)]4 as shown in Fig.
3.5. This is an example of a general type of structure called a cubane. (see Fig.3.7)

Cu

Cu

O
Cu

Cu

O
O

Fig. 3.7 Cubane Structure Of [(hfac)Cu(3-OR)]4

48

[(hfac)Cu(:3-OCH3)(THF)]4, for example, adopts a similar structure.3.10

Both [(hfac)Cu(:3-OCH2CH(OH)CH3)]4 and [(hfac)Cu(:3-OCH3)(THF)]4 adopt this
cubane structure.
The molecule [(hfac)Cu(:3-OCH2CH(OH)CH3)]4 consists of four Cu(hfac) units
triply linked together by the oxygen atoms from the diol groups. The Cu(II) ions are
sited in a nearly regular tetrahedron with Cu....Cu separations of 2.9764(16),
2.9734(15), and 2.9644(16) D. The coordination number around Cu(II) in this cubane is
5 and the geometry is roughly square pyramidal, where each propylene glycol alkoxo
oxygen atom triply bridges three Cu(II) ions.
3.4 Conclusions
From the above results we learned that bulky amines, especially tertiary amines,
give different adducts than the desired Cu(hfac)2(amine). Our purpose in this study was
to prepare neutral adducts and compare their efficiency as Cu-CVD precursors to the
hydrate or the alcohol adducts of the structure Cu(hfac)2L. With the bulky amines we
obtained ionic complexes which can not be used as CVD precursors. From the reaction
between Cu(hfac)2 and propylene glycol, we learned that this diol prefers to monocoordinate to Cu(II) in Cu(hfac)2 instead of chelate.
So when choosing amine ligands for Cu-CVD, in addition to the thermodynamic
aspects, one might consider other factors. It seems that bulky amines can hinder the
interaction of the amine with the metal center in Cu(hfac)2. Also, side products can
form easily when amines and their adducts are exposed to air and water.

49

3.5 References
3.1) James, A. M. Unpublished work.
3.2) Nozari, M. S.; Drago, R. S. Inorg. Chem., 1970, 9, 47-52.
3.3) Belford, R. C. E.; Fenton, D. E.; Truter, M. R. J. Chem. Soc., Dalton Trans, 1972,
2208-2213.
3.4) Belford, R. C. E.; Fenton, D. E.; Truter, M. R. J. Chem. Soc., Dalton Trans,
1974,17-23.
3.5) Chow, Y. L.; Danen, W. C.; Nelsen, S. F.; Rosenblatt, D. H. Chem. Rev., 1978,78,
243-274. Zheng; Z., Evans; D. H., Nelson; S. F., J. Org. Chem. 2000, 65,
1793-1798.
3.6) Smith, P. J.; Mann, C. K. J. Org. Chem., 1969, 34, 1821-1826.
3.7) Yufit, D. S.; Struchkov, Yu. T.; Garbuzova, I. A.; Chernoglazova, I. V.; Gololobov,
I. V. Russ. Chem. Bull., 1994, 43, 245-248.
3.8) Fan, H. Ph.D. Dissertation, Louisiana State University, 2000.
3.9) James, A. M. Ph.D. Dissertation, Louisiana State University, 1999.
3.10) Biedell, W.; Shklover, V.; Baker, H. Inorg. Chem., 1992, 31, 5561-5571.

50

Chapter 4
Tetrameric Copper(I) Amide Clusters
4.1 Introduction
An aspect that has been investigated in our lab is to develop a new class of
volatile Cu(I) complexes that do not belong to the (hfac)Cu(I) group. Since these
new complexes contain no oxygen or fluorine atoms, this makes them ideal as
Cu-depositing precursors. Al is known for being electropositive and for its high affinity
toward oxygen and fluorine, which make it very reactive toward hfac ligands. Thus,
Cu-CVD precursors without oxygen or fluorine may be very useful for depositing
Cu-Al alloys.4.1 Furthermore, it has been demonstrated in the literature that many
complexes of Cu(I) are photochemically active.4.2 If these complexes are volatile
enough, then it may be possible to utilize them as precursors for photochemical vapor
deposition. In photochemical vapor deposition, light is used as the energy source for
decomposing the gaseous reactants. Photons excite the reactant gases, which enhance
their chemical reactivity. Thus, the excited state may react faster or at a lower
temperature than the ground state.4.3
Currently, we are searching for volatile Cu(I) compounds with photochemical
activity as potential Cu-CVD precursors. Our goal is to deposit copper films from these
complexes utilizing light as a source of energy or combining light with heat to enhance
the thermal decomposition in thermal CVD. However, most of the Cu(I)
photochemically active complexes that are known in the literature are ionic and their
salts are not volatile.4.2

51

On the other hand, neutral copper amide compounds, such as [CuN(SiMe3)2]4, are
promising Cu-CVD precursors since they exhibit some volatility.4.4 It was reported by
our group that [CuN(SiMe3)2]4 is luminescent and volatile enough to be used as a
Cu-CVD precursor.4.5 This complex was reported as a precursor for depositing Cu
films at a substrate temperature of 275 C.4.6 In our group we succeeded in depositing
Cu films from [CuN(SiMe3)2]4 at substrate temperature of 145 C via thermal CVD
experiments under hydrogen. There are some slight improvements for the Cu
deposition when Xe arc lamp irradiation was applied during the CVD run.4.5 However,
this finding is inconclusive, and more investigation needs to be carried out regarding
whether or not light may offer enhancement for the thermal Cu CVD.
This chapter summarizes the study of the photoactivities of several Cu(I) amide
tetramers. These tetramers are: [CuN(SiMe3)2]4, [CuN(t-Bu)(SiMe3)]4, [CuN(i-Pr)2]4
and [CuNEt2]4.
4.2 Experimental
Chemicals were acquired from Aldrich Chemical Co. Solvents used were
anhydrous and deoxygenated. All reagents were used as received without further
purification. Syntheses were carried out in a drybox or in schlenk apparatus under
insert atmosphere.
4.2.1 [CuN(SiMe3)2]4
This compound was first prepared by Brger.4.7 In this study we prepared this
tetramer as follows: In the dry box, CuCl (4.949 g, 50 mmol) was placed in a flask that
was wrapped in foil to protect the CuCl from light. To this ether (50 mL) was added

52

and the suspension was stirred for an hour and a half. A solution of LiN(SiMe3)2 (1M;
55 mL, 55 mmol) in THF was added to the CuCl suspension. The mixture was left to
stir overnight. This was taken outside the dry box. This suspension was filtered over
Celite several times using warm pentane-DCM (1:1) mixture for rinsing until liquid was
clear. This was placed in the refrigerator for 24 hr. White solid developed from this
filtrate. H1 NMR (CDCl3, vs. TMS):, 0.42 ppm (200 MHz; lit. 0.34 ppm).4.5
4.2.2 [CuN(t-Bu)(SiMe3)]4
The study of this tetramer was started by James.4.5 She attempted to make this
compound and measure its phosphorescence. She observed luminescence that appeared
to be green at room temperature and orange at low temperature. In this study we aimed
to follow up on DFT calculations and to find out more about the orange vs. green
luminescence.
In the dry box 3.82 mL (0.0190 mol) of N-tert-butyl-trimethylsilylamine and
11.8 mL of a 1.6 M solution of butyllithium (0.0188 mol) in n-hexane were dissolved in
ether and stirred for an hour. In another flask, which was wrapped in foil, a suspension
of CuCl(0.989 g, 0.01 mol) in ether was stirred for an hour. The amine salt mixture was
added to the CuCl suspension and stirred for one hour. The reaction mixture was taken
outside the dry box and it was stirred for four hours under N2 at -10 C. Dark purple
solid resulted. The suspension was filtered over Celite several times using hexane for
rinsing. When the yellowish filtrate ran almost colorless, the solvent was evaporated to
half its volume and left in the refrigerator overnight. Colorless crystals formed.
However, the yield was minimal. These crystals were placed under a long-wave

53

(365 nm) UV lamp; two different colors of luminescence were observed: green and
orange. The two different crystals were separated by spatula and were analyzed by
X-ray. The crystals with green luminescence were of the structure given in (Fig.4.1).
The crystals with orange luminescence turned to blue powder and could not be
characterized further. The two products have similar solubility and sublimation
temperatures. Small quantities of the orange luminescent material could be separated
because it dissolves more readily in benzene than the green luminescent material. This
could not be adapted readily to a chromatographic separation, because the compounds
decompose on silica gel. However, we were able to partially separate the orange and
green luminescent products and obtain their phosphorescence spectra.

Fig. 4.1 ORTEP Drawing of [CuN(t-Bu)(SiMe3)]4

54

Table 4.1 Crystal Data For [CuN(t-Bu)(SiMe3)]4

Formula
C28H72Cu4N4Si4
Formula weight
831.42
a/
8.852(2)
b/
13.177(3)
c/
17.356(3)
$//
90.541(10)
V/3
2024.5(7)
3
Dcalc/g cm
1.364
Z
2
Space group
P2/n
T/K
120(1)
:/mm1
2.213
R(F) (all data)
0.095
Rw(F2) (all data)
0.195
Additional crystallographic data, and further data collection and refinement
parameters, are summarized in Appendix A.
The preparation of [CuN(t-Bu)(SiMe3)]4 was repeated using a different ratio of
reactants: 2.3 mL (0.012 mol) of N-tert-butyl-trimethylsilylamine, 6.9 mL of a 1.6 M
solution of butyllithium in n-hexane (0.011 mol), and 0.98 gram (0.01 mol) of CuCl.
The reaction was carried out by repeating the above steps. The same products were
obtained, but the orange product was more predominant.
In this study we were able to purify the compound of green luminescence
(via crystallization). We found that its luminescence is similar to that of other [CuNR2]4
compounds and the orange luminescence is due to impurity.
4.2.3 [CuN(i-Pr)2]4
In the dry box(LiN(i-Pr)2).THF (5.5 mL, 2M in heptane, 0.011 mol) was added
to a suspension of CuCl (0.98 g, 0.01 mol) in ether. This was stirred for 1.5 hr and then
placed in the refrigerator overnight. This produced a dark purple solid in the solution
55

mixture. The product mixture showed two different luminescences under the UV light:
orange and green. The solvent was evaporated which resulted in a mixture of white and
dark brown solid. The white solid was of green luminescent color under UV light and
the orange luminescence disappeared after the solvent evaporation. This white material
was separated via spatula and its emission spectra were measured under nitrogen.
4.2.4 [CuNEt2]4
This was prepared according to the literature.4.8
4.2.5 Luminescence Measurements
The phosphorescence data were collected using a Spex Instruments Fluorolog 2
model F112X spectrometer (Hamamatsu R636 photomultiplier). Spectra were
measured at room temperature and 77 K (cooling with Liq N2) for each tetramer.
4.3 Results
4.3.1 Preparations And Properties
Synthesis of the copper(I) amide tetramers was carried out by a metathesis
reaction on copper(I) halide, CuCl, and one equivalent of the appropriate lithium amide
in ether, except for [CuN(t-Bu)(SiMe3)]4 (see below), as in the following equation:
CuCl + Li[NR2]

1/4[CuNR2]4 + LiCl

(1)

The difficulty in obtaining pure product with a satisfactory yield can be

attributed to the formation of cuprate Li[Cu(NRR')2].4.9
We found that stirring the reactants for at least one hour and then placing the
reaction flask in the refrigerator in the dry box for 24 hr produces the desired tetramer.
We noticed the presence of the orange luminescent material in all tetramers
56

except for [CuN(SiMe3)2]4. We found that by varying the reactant ratios in the
preparation of [CuN(t-Bu)(SiMe3)]4, the synthesis may lead to the production of more
of the green or orange material. For example, we found that the producing more green
compound is parallel with the presence of more ligand. The products were difficult to
purify. Except for [CuN(SiMe3)2]4, the tetramers were isolated from impurity by
mechanical separation under UV light. This may be because [CuN(SiMe3)2]4 is more
stable than the others due to the bulky N(SiMe3)2 ligand.
The Cu(I) tetramers in this study are colorless crystalline complexes. Some of
these compounds showed stability in air, however, all compounds decomposed, over a
period of weeks, in solvents to blue solid. The luminescence behavior and the stability
of these complexes is summarized in Table ( 4.2).
Table 4.2 Luminescence Of Cu(I) Tetramers And Their
Stability
Compound

Luminescence

Stability in air

[CuN(SiMe3)2]4

bright green

stable

[CuN(t-Bu)(SiMe3)]4 (I )

green

stable

"[CuN(t-Bu)(SiMe3)]"n (II)

orange

stable

[CuN(iPr)2]4

green

not stable

[CuNEt2]4

green

not stable

57

The solid state emisson maxima, 8em (M-M) are given in table 4.3.
Table 4.3 Estimated 8em Max For Phosphorescence(nm)
Compound

300 K

77 K

[CuN(SiMe3)2]4

512

525

[CuN(t-Bu)(SiMe3)]4 (I )

510

532

"[CuN(t-Bu)(SiMe3)]"n (II)

595

625

[CuN(iPr)2]4

560

600

[CuNEt2]4

545

-550

4.3.1.1 Structure Of Related Tetramers

A comparison of structural parameters in Cu(I) amide tetramers is summarized
in table (4.4).
Table 4.4 Structural Parameters Of Cu(I) Amido Tetramers:
Tetramer

Cu...Cu D

Cu-N D

N-Cu-N

Cu-N-Cu

[CuNMe2]44.9

2.702(2)

1.890(5)

178.5(2)

91.2(2)

[CuNEt2]44.8

2.664(2)

1.904(3)

175.4(1)

88.8(1)

[CuNC4H8]44.9

2.717(2)

1.885(4)

177.1(2)

92.2(2)

[CuNSiMe3But]4

2.714(8)

1.941(2)

178.4(10)

89.0(14)

[CuN(SiMe3)2]44.5

2.6937(7)

1.925(4)

179.0(1)

88.3(1)

[CuNMe((CH2)2NMe2)]44.9

2.618

1.913

169.4

86.1

The examples that are provided in this table show that the average separation
between two neighboring copper atoms (2.702(2) D) is very close to those found in
alkoxo and alkyl derivatives. For instance, [Cu(OBut)]4 has a Cu...Cu separation of
2.709(3) D, where [CuNEt2]4 has a Cu...Cu distance of 2.664(2) D.4.8 However, these
separation distances are considerably longer than those in organometallic derivatives
58

(e.g. [Cu(CH2SiMe3)]4, Cu...Cu 2.418(2) D), indicating that the Cu...Cu separation is
greatly affected by bridging. In the examples presented in table (4.4) it seems that the
tetramers are held together by ligand donor participation. Both of the ligands, alkoxide
and amide, have two or more lone pairs which may behave as the donors.
An alkyl group, on the other hand, has only one pair of electrons available to bond the
two metal centers. Essentially, the bond between the carbon atom and the two Cu
centers is a 3-center-2-electron bond. This makes the Cu-C-Cu angle the smallest of the
three.(Fig.4.2)

R
O

H2
N
Cu

Cu

Cu

R3
C
Cu

Cu

Cu

Fig. 4.2 The Separation Between Cu...Cu Is

Affected By The Ligand Type
Therefore, the longer Cu...Cu distance can be attributed to the fact that the
tetramer is held by donor bonds while minimal or no d10-d10 Cu-Cu interaction is
involved. In the amide tetramers, Cu-N-Cu angles are close to 90. Accordingly,
nitrogen is in an approximately tetrahedral environment and the Cu4N4 core is perfectly
planar.
4.3.2 Phosphorescence Spectra
Appendix B represents the phosphorescence spectra we obtained for the
tetramers in this study. We have included the phosphorescence spectrum of

59

[CuN(SiMe3)]4 which was performed by another member of our group for comparison.4.5
4.4 Discussion
4.4.1 Spectroscopic Properties
The evaluation of the electronic structure of metal complexes reveals a basic
difference between the d1-9 and d10 configurations. This difference arises from the fact
those d-d transitions cannot occur in d10 systems.4.3 Therefore, in d10 complexes such as
Cu(I), only MLCT and metal localized transitions are possible. Metal-to-ligand charge
transfer (MLCT) transitions result from the outward flow of electron density from a
metal orbital to ligand-based orbital.
There are two types of metal localized transitions in d10 complexes: one type
involves a transition from (n-1)d10 to (n-1)d9ns1, and the other from (n-1)d10 to (n1)d9np1. Metal centered transitions result in a change in the principal quantum number,
n, which is not allowed. Therefore, this type of absorption is typically of low
intensity.4.3
The absorption of light by a molecule causes it to experience a transition from
an electronic ground state (GS) to an electronic excited state (ES). It is conceivable that
with the altered electron arrangement, the excited state will have different equilibrium
geometry than the ground state.
According to the Franck-Condon principle, the electronic transition is very rapid
compared to the speed of vibrational nuclear motion. Therefore, the ES will be in a
vibrationally excited (i.e. non-equilibrium) geometry, corresponding to a vibrational ES
of the electronic excited state.

60

The emission from the excited state occurs either with the same spin as that of
the ground state, fluorescence, or with a different spin from the ground state,
phosphorescence. The later is produced by an intersystem crossing and it is not
allowed by the spin selection rule. Thus, phosphorescence lifetimes are usually much
longer than fluorescence lifetimes. Accordingly, phosphorescence is more likely to be
useful in photo-induced CVD.
Emission usually occurs at lower energy because it returns the molecule to a
vibrational excited state of the electronic ground state. The energy difference between
an absorption peak and the corresponding emission is known as the Stokes shift. The
magnitude of the Stokes shift is a fairly sensitive guide to the geometric differences
between GS and ES.
When it comes to Cu(I) luminescent clusters, one of the questions that emerge is
the extent of metal-metal interaction in the relevant excited state. Holt and coworkers
conducted studies for a series of [CuIL]4 (cubanes) in an attempt to answer this
question.4.10
Table 4.5 Solid State Emission Maxima4.10
Cluster

Cu-Cu
(D)

8em (MLCT)

8em (M-M)

(nm)

X-Cu-X
deg

Cu-X-Cu
deg

[CuIpy]4

2.691(5)

436

615

110.9-120.2(1)

57.7-61.1(1)

[CuIpip]4

2.657(2)

---

570

113.48(4)

58.93(5)

[CuIpy]4

2.875(2)

449

---

104.0-115(1)

65.3-104.0(1)

[CuICH3CN]4

3.022(10)4.298(13)

540

---

107.0-111.5(3)

69.0(2)--107.0(4)

(nm)

61

For the clusters in table (4.4) the angles at copper are nearly constant regardless of the
differences in the bulk of the ligands.
They concluded that only those with ground state of Cu-Cu distances less than
the Cu(I) van der Waals radii (2.8 D) display the lower energy ("M-M*") emission.
This study concluded that the emissions in the range 550-680 nm are due to metal
localized ("M-M") transition. This assignment derives from the fact that the absorption
is absent in polymeric systems of the same stoichiometry and ligand identity where
Cu-Cu separation is longer.4.10 From this table we learned that one method of
understanding our luminescence is by examining M-M distance. This table presents
two groups of luminescent Cu(I) compounds. The groups are of short and long M-M
distances. We found that our compounds have shorter M-M distance, which is
consistent with M-centered luminescence.
Hoffmann et al. 4.11 carried out a molecular orbital calculations on Cu(I) model
systems. He has shown that Cu4+4 clusters with Cu-Cu distances of 2.8 D have a
binding energy of -0.417 eV, and that the bonding strength increases as the Cu-Cu
distances decreased. The binding energy is -0.984 eV at a Cu-Cu distance of 2.57 D. A
model dimeric system ([Cu(CH2)2PH2]2) gave a computed optimum Cu-Cu distance of
2.7 D with Cu-Cu orbital overlap population increasing as the Cu-Cu separation
decreased. This study confirmed that a Cu...Cu distance of 2.8 D or less is an indication
of Cu-Cu interaction.
In our laboratory we have established a good familiarity with the tetramer
[CuN(SiMe3)2]. We found that this tetramer has two absorption maxima

62

(at 283 and 246 nm) and emits intense blue-green luminescence when the compound is
excited at wavelengths below 400 nm.4.6 In the current study we found that the
tetramers we focused on behave in an analogous manner.
In the molecular orbital model of the bonding within the square-planar (D4h) Cu4
group of [CuN(R)2], each copper atom utilizes one d and s orbital in a F bonding to the
ligands. Mixing 3dxyand 4s and 4px orbitals, stabilizes the occupied eu orbital and
increases stability of the cluster. The molecular orbital energy diagram in Fig. 4.3
illustrates that the HOMOs are 4a2g and 12eu, and the LUMO is 9a1g.

Fig. 4.3 MO Diagram For [CuN(SiH3)2]4

A density-functional theory calculation on [CuN(SiH3)2] suggested that the LUMO

contains a significant contribution from the bonding combination of Cu 4p orbitals.4.12

63

9a1g: 16%

Cu

z x
y

Cu

Cu

Cu

13%
N

Cu

z x
y

Cu

Cu

Cu

Fig 4.4 Two M-M Bonding Contributions

To The LUMO In [CuN(SiCH3)2]4
We proposed that the excited state in the cluster results from the a2g to a1g
(i.e. HOMO LUMO) orbital transition. The one electron elevation from an
antibonding to a bonding orbital causes the overall bond order within the cluster core to
increase with accompaniment decrease in Cu...Cu distance.
The large Stokes shifts (excitation 300-320 nm; emission 520-550 nm) suggest
a big difference in the geometry between the ground and excited states of the tetramers.
Population of 4px orbitals delocalized over the Cu4 core should lead to enhanced
Cu...Cu bonding and, accordingly, to less Cu-N bonding. Hence, this excited state

64

should be significantly distorted from the ground state, i.e., the HOMO-LUMO
excitation should lead to enhanced intermetallic bonding, and the structure should
contract.
4.5 Conclusions
The work presented in this chapter was begun by a previous member of our
group.4.5 In this study we found that these tetramers have fair stability in air when
SiMe3 is present in the ligand. The fact that some of these tetramers are air stable,
sublimable and luminescent indicates that these compounds are potential precursors for
photochemical CVD.
4.6 References
4.1) Eiichi, K.; Yumiko, K.; Nobuyuki, T.; Tomohiro, O. J. Electrochem. Soc.,1994,
3494-3499.
4.2) Kutal, C. Coord. Chem. Rev. 1990, 99, 213-252.
4.3) Elliott, D. J. Integrated Circuit Fabrication Technology, Second Edition, 1989,
McGraw-Hill Publishing Company, New York.;chapter 1.
4.4) Lappert, M. F.; Power, P. P.; Sanger, A. R.; Srivastava, R. C. Metal and
Metalloid Amides. Horwood: Chichester, England, 1980.
4.5) James, A. M.; Laxman, R. K.; Fronczek, F. R.; Maverick, A. W. Inorg. Chem.,
1998, 37, 3785-3791.
4.6) Baxter, D. V.; Chisholm, M. H.; Gama, G. J.; Hector, A. L.; Parkin, I. P. Adv.
Mater. 1995, 7, 49-51.
4.7) Brger, H.; Wannagat, U. Monatsh. Chem. 1964, 95, 1099-1102.
4.8) Hope; H., Power; P. P., Inorg. Chem. 1984, 23, 936-937.
4.9) Gambarotta. S.; Bracci, M.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. J. Chem.
Soc., Dalton Trans. 1987, 1883-1888.

65

4.10) Rath, N. P.; Holt, E. M.; Tanimura, K. Inorg. Chem. 1985, 24, 3934-3938.
4.11) Mehrotra, P.; Hoffmann, R. Inorg. Chem. 1978, 17, 2187-2189.
4.12) Brett, C. M. M. S. Thesis, Ohio State University, 2000. Brett, C. M.; Bursten,
B. E. Unpublished work.

66

Chapter 5
Conclusions And Future Work
5.1 Introduction
In this dissertation we tried to explore different aspects that are related to
Cu-CVD precursors. This thesis researched the quality of Cu(hfac)2(amine) adducts as
well as the potential of the luminescent [CuNR2]4 as Cu-CVD precursors.
5.2 Cu(hfac)2(amine) Adducts
Chapter 2 described the synthesis and the characterization of a series of
Cu(hfac)2(amine) adducts. From the synthesis we discovered that some of these adducts
are difficult to isolate.
The study of these adducts as Cu-CVD precursors under hydrogen showed some
improvement for (Cu(hfac)2(allylamine)2) in the deposition rate compared to the alcohol
adducts. The study of the same adducts under the inert gas nitrogen proved that these
adducts are self-reducing precursors. However, we learned that when H2 is present it
acts as the principal reducing agent.
The amine adducts were more stable than the alcohol ones, and no excess of
amine vapor was needed during the CVD reactions. Also we found that the
Cu(hfac)2(amine)-based Cu films adhere better to the glass substrate than those
deposited using Cu(hfac)2(H2O).
Chapter 3 showed that the bulky amines are not a good choice for synthesizing
Cu(hfac)2(amine) adducts. The reactions between Cu(hfac)2 and bulky amines resulted
in several different types of ionic complexes.

67

Also the reaction of Cu(hfac)2 with propylene glycol did not result in the desired
compound (Cu(hfac)2(propylene glycol)2; instead we obtained a cubane. This result
agrees with James's result that these diols ligands prefer binding in monodentate
fashion to Cu(hfac)2, rather than bidentate.5.1
5.3 [CuNR2]4
In chapter 4 we found that the tetramers that were studied are luminescent and
some of them are volatile enough to function as copper thermal or photochemical vapor
deposition precursors. In this thesis we investigated the photo behavior of these
tetramers both at room temperature and at 77K. We attributed the big Stokes shift
between the absorption and the emission maxima to the difference in the geometry
between the ground and excited states. We found that when the bulky SiMe3 group is
present in the ligand this contributes to the stability of the tetramers and make it
possible to handle this tetramer in air. However, all these tetramers were at least
somewhat air-sensitive in solution.
The isolation of these tetramers proved to be a challenging task, thus, there is a
room here for future work in this regard. In addition, we were not able to study these
tetramers as Cu-CVD precursors. This was due to the fact that our lab is currently not
equipmed to perform this study. The design of photo CVD or thermal and photo CVD
reactor for depositing Cu films from these tetramers remains a future work to be
accomplished.

68

5.4 Reference
5.1) James, A. M. Ph.D. Dissertation, Louisiana State University, 1999.

69

Appendix A
Crystal Data
This appendix consists of tables of x-ray crystal structure data in CIF formats.
Table A-1.CIF File For Cu(hfac)2(pyrrolidine)
_chemical_name_systematic
;
bis(1,1,1,5,5,5-hexafluoropentanedionato)(pyrrolidine)copper(II)
;
_chemical_name_common
?
_chemical_formula_moiety
'C14H11NO4F12Cu'
_chemical_formula_structural
?
_chemical_formula_analytical
?
_chemical_formula_sum
'C14H11NO4F12Cu'
_chemical_formula_weight
548.77
_chemical_melting_point
?
_chemical_compound_source
?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C ? 0.002 0.002 International_Tables_Vol_IV_Table_2.3.1
H ? 0.000 0.000 International_Tables_Vol_IV_Table_2.3.1
N ? 0.004 0.003 International_Tables_Vol_IV_Table_2.3.1
O ? 0.008 0.006 International_Tables_Vol_IV_Table_2.3.1
F ? 0.014 0.010 International_Tables_Vol_IV_Table_2.3.1
Cu ? 0.263 1.266 International_Tables_Vol_IV_Table_2.3.1
CRYSTAL DATA
_symmetry_cell_setting
triclinic
_symmetry_space_group_name_H-M
'P-1'
_symmetry_space_group_name_Hall '-P 1'
loop_
_symmetry_equiv_pos_as_xyz
'x,y,z'
-x,-y,-z
_cell_length_a
9.0201(13)
_cell_length_b
9.8876(9)
70

_cell_length_c
11.4485(6)
_cell_angle_alpha
66.872(7)
_cell_angle_beta
83.297(11)
_cell_angle_gamma
87.452(12)
_cell_volume
932.6(2)
_cell_formula_units_z
2
_cell_measurement_temperature
100
_cell_measurement_reflns_used
25
_cell_measurement_theta_min
12.0
_cell_measurement_theta_max
23.0
_cell_special_details
;?
;
_exptl_crystal_description
fragment
_exptl_crystal_colour
'emerald green'
_exptl_crystal_size_max
0.58
_exptl_crystal_size_mid
0.50
_exptl_crystal_size_min
0.45
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn
1.954
_exptl_crystal_density_method
'none'
_exptl_crystal_F_000
542
_exptl_absorpt_coefficient_mu 1.309
_exptl_absorpt_correction_type psi_scans_(North,_Phillips,_Mathews,_1968)
_exptl_absorpt_correction_T_min 0.8327
_exptl_absorpt_correction_T_max 1.0000
EXPERIMENTAL DATA
_diffrn_special_details
;?
;
_diffrn_ambient_temperature
100
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
Mo-K\a
_diffrn_radiation_source
sealed_tube
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device
Enraf_Nonius_CAD4
_diffrn_measurement_method
\q/2\q
_diffrn_standards_number
3
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time 60
71

_diffrn_standards_decay_%

0.7

loop_
_diffrn_standard_refln_index_h
_diffrn_standard_refln_index_k
_diffrn_standard_refln_index_l
? ? ?
? ? ?
? ? ?
_diffrn_reflns_number
7628
_diffrn_reflns_av_R_equivalents 0.015
_diffrn_reflns_av_sigmaI/netI
1.000
_diffrn_reflns_limit_h_min
-12
_diffrn_reflns_limit_h_max
8
_diffrn_reflns_limit_k_min
-13
_diffrn_reflns_limit_k_max
13
_diffrn_reflns_limit_l_min
-16
_diffrn_reflns_limit_l_max
15
_diffrn_reflns_theta_min
2.5
_diffrn_reflns_theta_max
30.0
_reflns_number_total
5425
_reflns_number_observed
5183
_reflns_observed_criterion
>1.0\s(I)
_computing_data_collection
'CAD4_(Enraf-Nonius,_1994)'
_computing_cell_refinement
CAD4_(Enraf-Nonius,_1994)
_computing_data_reduction
'process_MolEN_(Fair,_1990)'
_computing_structure_solution
Direct_methods_(MULTAN,_Main_et_al.,_1980)
_computing_structure_refinement LSFM_MolEN_(Fair,_1990)
_computing_molecular_graphics
?
_computing_publication_material BTABLE_PTABLE_CIF_IN_MolEN_(Fair,_1990)
REFINEMENT DATA
_refine_ls_structure_factor_coef F
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
'4Fo^2^/(\s^2^(Fo^2^) + 0.0004 Fo^4^)'
_refine_ls_hydrogen_treatment
mixed
_refine_ls_extinction_method
isotropic_(Zachariasen,_1963)
_refine_ls_extinction_coef
3.7(7)E-7
_refine_ls_abs_structure_Flack ?
_refine_ls_number_reflns
5183
_refine_ls_number_parameters
335
_refine_ls_number_restraints
0
_refine_ls_number_constraints
0
72

_refine_ls_abs_structure_details
;?
;
_refine_ls_R_factor_all
0.032
_refine_ls_R_factor_obs
0.030
_refine_ls_wR_factor_all
0.038
_refine_ls_wR_factor_obs
0.038
_refine_ls_goodness_of_fit_all 1.993
_refine_ls_goodness_of_fit_obs 1.990
_refine_ls_shift/esd_max
0.003
_refine_ls_shift/esd_mean
0.000
_refine_diff_density_max
0.576
_refine_diff_density_min
-0.237
ATOMIC COORDINATES AND THERMAL PARAMETERS
loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_occupancy
_atom_site_thermal_displace_type
_atom_site_calc_flag
_atom_site_calc_attached_atom
_atom_site_type_symbol
Cu1 0.09532(2) 0.04024(2) 0.34497(1) 0.01308(6) 1.000 Uij ? ? Cu
F1 0.1307(1) -0.5309(1) 0.6208(1) 0.0262(4) 1.000 Uij ? ? F
F2 -0.0720(1) -0.4097(1) 0.6239(1) 0.0277(4) 1.000 Uij ? ? F
F3 0.1084(1) -0.3875(1) 0.72161(9) 0.0276(4) 1.000 Uij ? ? F
F4 0.4577(1) -0.1470(1) 0.09958(8) 0.0239(4) 1.000 Uij ? ? F
F5 0.4992(1) -0.3394(1) 0.2640(1) 0.0470(6) 1.000 Uij ? ? F
F6 0.3120(2) -0.3327(1) 0.1616(1) 0.0630(5) 1.000 Uij ? ? F
F7 0.1718(2) 0.3505(1) -0.06284(9) 0.0333(5) 1.000 Uij ? ? F
F8 0.3749(1) 0.4394(2) -0.0453(1) 0.0422(6) 1.000 Uij ? ? F
F9 0.1652(2) 0.5273(1) 0.0003(1) 0.0363(6) 1.000 Uij ? ? F
F10 0.5040(1) 0.1363(1) 0.5059(1) 0.0313(4) 1.000 Uij ? ? F
F11 0.3680(1) 0.3230(1) 0.4960(1) 0.0449(4) 1.000 Uij ? ? F
F12 0.5533(1) 0.3439(1) 0.3531(1) 0.0357(5) 1.000 Uij ? ? F
O1 0.0875(1) -0.1471(1) 0.49688(9) 0.0152(4) 1.000 Uij ? ? O
O2 0.2743(1) -0.0583(1) 0.2482(1) 0.0191(4) 1.000 Uij ? ? O
O3 0.1172(1) 0.2121(1) 0.18399(9) 0.0168(4) 1.000 Uij ? ? O
73

O4 0.2434(1) 0.1170(1) 0.41673(9) 0.0159(4) 1.000 Uij ? ? O

N1 -0.0916(1) -0.0152(1) 0.2976(1) 0.0166(4) 1.000 Uij ? ? N
C1 0.1360(2) -0.2701(1) 0.4961(1) 0.0145(5) 1.000 Uij ? ? C
C2 0.2289(2) -0.3010(1) 0.4056(1) 0.0179(5) 1.000 Uij ? ? C
C3 0.2916(2) -0.1924(1) 0.2890(1) 0.0171(5) 1.000 Uij ? ? C
C4 0.0770(2) -0.4016(1) 0.6166(1) 0.0172(5) 1.000 Uij ? ? C
C5 0.3923(2) -0.2528(2) 0.2021(1) 0.0241(6) 1.000 Uij ? ? C
C6 0.2297(2) 0.2942(1) 0.1475(1) 0.0159(5) 1.000 Uij ? ? C
C7 0.3422(2) 0.3024(1) 0.2185(1) 0.0181(5) 1.000 Uij ? ? C
C8 0.3342(2) 0.2186(1) 0.3487(1) 0.0158(5) 1.000 Uij ? ? C
C9 0.2357(2) 0.4043(2) 0.0077(1) 0.0215(6) 1.000 Uij ? ? C
C10 0.4420(2) 0.2561(1) 0.4260(1) 0.0200(5) 1.000 Uij ? ? C
C11 -0.2096(2) 0.0995(2) 0.2574(1) 0.0241(6) 1.000 Uij ? ? C
C12 -0.3118(2) 0.0455(2) 0.1882(2) 0.0334(7) 1.000 Uij ? ? C
C13a -0.2236(3) -0.0771(3) 0.1565(2) 0.033(1) 0.667 Uij ? ? C
C13b -0.1988(6) -0.0008(6) 0.1058(4) 0.035(2) 0.333 Uij ? ? C
C14 -0.0700(2) -0.0718(2) 0.1931(2) 0.0315(6) 1.000 Uij ? ? C
H1N -0.133(2) -0.078(2) 0.364(2) 0.025(5) 1.000 Uiso ? ? H
H2 0.248(2) -0.393(2) 0.418(2) 0.030(5) 1.000 Uiso ? ? H
H7 0.417(2) 0.367(2) 0.181(2) 0.023(5) 1.000 Uiso ? ? H
H11b -0.259(2) 0.117(2) 0.331(2) 0.030(5) 1.000 Uiso ? ? H
H11a -0.167(2) 0.188(2) 0.200(2) 0.030(5) 1.000 Uiso ? ? H
H12b -0.385(3) -0.007(3) 0.243(3) 0.074(9) 1.000 Uiso ? ? H
H12a -0.347(3) 0.119(2) 0.124(2) 0.054(8) 1.000 Uiso ? ? H
H14a 0.004(3) -0.005(2) 0.129(2) 0.052(7) 1.000 Uiso ? ? H
H14b -0.044(3) -0.166(2) 0.221(2) 0.047(7) 1.000 Uiso ? ? H
H13a1 -0.2197 -0.0574 0.0681 0.0394 0.667 Uiso calc C13a H
H13a2 -0.2684 -0.1705 0.2048 0.0394 0.667 Uiso calc C13a H
H13b1 -0.1628 0.0815 0.0320 0.0424 0.333 Uiso calc C13b H
H13b2 -0.2400 -0.0707 0.0807 0.0424 0.333 Uiso calc C13a H
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
_atom_site_aniso_type_symbol
Cu1 0.01434(7) 0.01313(6) 0.01187(6) -0.00255(5) -0.00102(5) -0.00167(4) Cu
F1 0.0461(6) 0.0136(3) 0.0287(4) 0.0046(4) 0.0121(4) -0.0019(3) F
F2 0.0222(4) 0.0245(4) 0.0390(5) -0.0081(4) 0.0045(4) -0.0010(4) F
74

F3 0.0550(6) 0.0260(4) 0.0147(4) -0.0072(4) -0.0046(4) -0.0025(3) F

F4 0.0270(4) 0.0288(4) 0.0177(3) -0.0035(4) 0.0065(3) -0.0071(3) F
F5 0.0626(7) 0.0551(6) 0.0301(5) 0.0389(5) 0.0106(5) -0.0013(4) F
F6 0.0699(7) 0.0605(4) 0.0591(5) -0.0385(5) 0.0333(5) -0.0484(3) F
F7 0.0731(8) 0.0308(4) 0.0164(4) -0.0143(5) -0.0069(4) -0.0042(3) F
F8 0.0402(6) 0.0799(9) 0.0234(5) -0.0230(6) 0.0105(5) 0.0052(6) F
F9 0.0829(9) 0.0210(4) 0.0275(5) 0.0137(5) -0.0119(5) -0.0024(4) F
F10 0.0335(5) 0.0222(4) 0.0412(5) 0.0016(4) -0.0213(4) -0.0068(3) F
F11 0.0334(5) 0.0522(4) 0.0519(4) 0.0104(4) -0.0143(4) -0.0407(3) F
F12 0.0300(5) 0.0399(5) 0.0381(5) -0.0203(4) -0.0067(4) -0.0038(4) F
O1 0.0181(4) 0.0136(3) 0.0142(4) -0.0006(3) -0.0007(3) -0.0032(3) O
O2 0.0205(5) 0.0178(4) 0.0190(4) -0.0006(4) 0.0028(4) -0.0038(3) O
O3 0.0200(4) 0.0157(4) 0.0151(4) -0.0019(3) -0.0011(3) -0.0016(3) O
O4 0.0161(4) 0.0156(4) 0.0160(4) -0.0023(3) -0.0008(3) -0.0038(3) O
N1 0.0184(5) 0.0177(4) 0.0141(4) -0.0030(4) -0.0019(4) -0.0035(3) N
C1 0.0161(5) 0.0141(4) 0.0136(5) -0.0021(4) -0.0017(4) -0.0029(4) C
C2 0.0208(6) 0.0151(5) 0.0183(5) -0.0008(5) 0.0010(5) -0.0054(4) C
C3 0.0161(6) 0.0198(5) 0.0156(5) -0.0005(4) -0.0005(4) -0.0071(4) C
C4 0.0221(6) 0.0136(5) 0.0171(5) -0.0005(5) 0.0017(5) -0.0038(4) C
C5 0.0312(8) 0.0221(6) 0.0201(6) -0.0009(6) 0.0066(6) -0.0077(4) C
C6 0.0201(6) 0.0139(5) 0.0142(5) 0.0006(4) 0.0029(5) -0.0030(4) C
C7 0.0186(6) 0.0164(5) 0.0196(5) -0.0045(5) 0.0035(5) -0.0045(4) C
C8 0.0138(5) 0.0145(4) 0.0196(5) 0.0001(4) -0.0005(4) -0.0069(4) C
C9 0.0315(7) 0.0209(6) 0.0152(5) -0.0052(5) 0.0024(5) -0.0023(4) C
C10 0.0186(6) 0.0177(5) 0.0242(6) -0.0013(5) -0.0039(5) -0.0069(4) C
C11 0.0195(6) 0.0260(6) 0.0278(6) 0.0026(5) -0.0060(5) -0.0123(4) C
C12 0.0232(7) 0.0470(7) 0.0341(6) 0.0054(6) -0.0113(5) -0.0230(5) C
C13a 0.027(1) 0.0375(9) 0.0353(9) 0.0003(9) -0.0093(8) -0.0221(7) C
C13b 0.028(2) 0.053(2) 0.028(2) 0.012(2) -0.011(2) -0.027(1) C
C14 0.0271(7) 0.0335(6) 0.0344(6) 0.0042(5) -0.0077(5) -0.0234(4) C
MOLECULAR GEOMETRY
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O1 1.9780(8) . . ?
Cu1 O2 2.253(1) . . ?
Cu1 O3 1.9515(8) . . ?
Cu1 O4 1.967(1) . . ?
75

Cu1 N1 1.992(1) . . ?
F1 C4 1.332(2) . . ?
F2 C4 1.341(2) . . ?
F3 C4 1.327(2) . . ?
F4 C5 1.322(2) . . ?
F5 C5 1.332(2) . . ?
F6 C5 1.335(2) . . ?
F7 C9 1.318(2) . . ?
F8 C9 1.327(2) . . ?
F9 C9 1.325(2) . . ?
F10 C10 1.328(2) . . ?
F11 C10 1.333(2) . . ?
F12 C10 1.330(2) . . ?
O1 C1 1.278(2) . . ?
O2 C3 1.229(2) . . ?
O3 C6 1.253(2) . . ?
O4 C8 1.263(1) . . ?
N1 C11 1.493(2) . . ?
N1 C14 1.497(2) . . ?
N1 H1N 0.83(2) . . ?
C1 C2 1.375(2) . . ?
C1 C4 1.536(2) . . ?
C2 C3 1.417(2) . . ?
C2 H2 0.87(2) . . ?
C3 C5 1.542(2) . . ?
C6 C7 1.396(2) . . ?
C6 C9 1.539(2) . . ?
C7 C8 1.387(2) . . ?
C7 H7 0.89(2) . . ?
C8 C10 1.535(2) . . ?
C11 C12 1.520(3) . . ?
C11 H11b 0.97(2) . . ?
C11 H11a 0.93(2) . . ?
C12 C13a 1.559(4) . . ?
C12 C13b 1.487(6) . . ?
C12 H12b 0.88(2) . . ?
C12 H12a 0.89(2) . . ?
C13a C13b 0.773(5) . . ?
C13a C14 1.502(3) . . ?
C13a H13a1 0.95 . . ?
C13a H13a2 0.95 . . ?
C13b C14 1.578(5) . . ?
C13b H13a1 0.868(7) . . ?
C13b H13b1 0.95 . . ?
76

C13b H13b2 0.95 . . ?

C14 H14a 0.98(2) . . ?
C14 H14b 0.89(2) . . ?
loop_
_geom_contact_atom_site_label_1
_geom_contact_atom_site_label_2
_geom_contact_distance
_geom_contact_site_symmetry_1
_geom_contact_site_symmetry_2
_geom_contact_publ_flag
? ? ? ? ? ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_2
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Cu1 O2 88.57(4) . . . ?
O1 Cu1 O3 173.03(5) . . . ?
O1 Cu1 O4 89.98(4) . . . ?
O1 Cu1 N1 89.79(4) . . . ?
O2 Cu1 O3 84.64(4) . . . ?
O2 Cu1 O4 92.05(4) . . . ?
O2 Cu1 N1 102.75(5) . . . ?
O3 Cu1 O4 91.84(4) . . . ?
O3 Cu1 N1 90.16(4) . . . ?
O4 Cu1 N1 165.19(5) . . . ?
Cu1 O1 C1 124.69(9) . . . ?
Cu1 O2 C3 120.10(9) . . . ?
Cu1 O3 C6 123.16(9) . . . ?
Cu1 O4 C8 123.0(1) . . . ?
Cu1 N1 C11 117.6(1) . . . ?
Cu1 N1 C14 115.1(1) . . . ?
Cu1 N1 H1N 105(1) . . . ?
C11 N1 C14 104.2(1) . . . ?
C11 N1 H1N 102(1) . . . ?
C14 N1 H1N 110(1) . . . ?
O1 C1 C2 130.4(1) . . . ?
O1 C1 C4 112.6(1) . . . ?
77

C2 C1 C4 116.9(1) . . . ?
C1 C2 C3 123.8(1) . . . ?
C1 C2 H2 118(1) . . . ?
C3 C2 H2 117(1) . . . ?
O2 C3 C2 128.6(1) . . . ?
O2 C3 C5 116.7(1) . . . ?
C2 C3 C5 114.7(1) . . . ?
F1 C4 F2 106.8(1) . . . ?
F1 C4 F3 107.4(1) . . . ?
F1 C4 C1 113.9(1) . . . ?
F2 C4 F3 107.0(1) . . . ?
F2 C4 C1 110.1(1) . . . ?
F3 C4 C1 111.3(1) . . . ?
F4 C5 F5 107.6(1) . . . ?
F4 C5 F6 107.2(1) . . . ?
F4 C5 C3 112.5(1) . . . ?
F5 C5 F6 107.4(1) . . . ?
F5 C5 C3 111.6(1) . . . ?
F6 C5 C3 110.3(1) . . . ?
O3 C6 C7 128.5(1) . . . ?
O3 C6 C9 113.8(1) . . . ?
C7 C6 C9 117.6(1) . . . ?
C6 C7 C8 120.6(1) . . . ?
C6 C7 H7 119(1) . . . ?
C8 C7 H7 119(1) . . . ?
O4 C8 C7 128.7(1) . . . ?
O4 C8 C10 113.3(1) . . . ?
C7 C8 C10 117.9(1) . . . ?
F7 C9 F8 107.2(1) . . . ?
F7 C9 F9 107.7(1) . . . ?
F7 C9 C6 111.5(1) . . . ?
F8 C9 F9 107.7(1) . . . ?
F8 C9 C6 111.9(1) . . . ?
F9 C9 C6 110.5(1) . . . ?
F10 C10 F11 107.3(1) . . . ?
F10 C10 F12 106.7(1) . . . ?
F10 C10 C8 111.7(1) . . . ?
F11 C10 F12 107.9(1) . . . ?
F11 C10 C8 109.8(1) . . . ?
F12 C10 C8 113.1(1) . . . ?
N1 C11 C12 105.6(1) . . . ?
N1 C11 H11b 110(1) . . . ?
N1 C11 H11a 110(1) . . . ?
C12 C11 H11b 114(1) . . . ?
78

C12 C11 H11a 107(1) . . . ?

H11b C11 H11a 107(1) . . . ?
C11 C12 C13a 106.0(2) . . . ?
C11 C12 C13b 100.0(3) . . . ?
C11 C12 H12b 109(2) . . . ?
C11 C12 H12a 112(1) . . . ?
C13a C12 C13b 29.3(2) . . . ?
C13a C12 H12b 100(1) . . . ?
C13a C12 H12a 116(1) . . . ?
C13b C12 H12b 128(2) . . . ?
C13b C12 H12a 94(1) . . . ?
H12b C12 H12a 111(2) . . . ?
C12 C13a C13b 70.2(5) . . . ?
C12 C13a C14 104.5(2) . . . ?
C12 C13a H13a1 110.7 . . . ?
C12 C13a H13a2 110.7 . . . ?
C14 C13a H13a1 110.7 . . . ?
C14 C13a H13a2 110.7 . . . ?
H13a1 C13a H13a2 109.5 . . . ?
C12 C13b C13a 80.5(5) . . . ?
C12 C13b C14 104.3(3) . . . ?
C12 C13b H13b1 110.8 . . . ?
C12 C13b H13b2 110.7 . . . ?
C14 C13b H13b1 110.7 . . . ?
C14 C13b H13b2 110.8 . . . ?
H13b1 C13b H13b2 109.5 . . . ?
N1 C14 C13a 105.4(2) . . . ?
N1 C14 C13b 105.8(3) . . . ?
N1 C14 H14a 104(1) . . . ?
N1 C14 H14b 112(1) . . . ?
C13a C14 H14a 118(1) . . . ?
C13a C14 H14b 101(1) . . . ?
C13b C14 H14a 91(1) . . . ?
C13b C14 H14b 125(1) . . . ?
H14a C14 H14b 113(1) . . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
79

_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O2 Cu1 O1 C1 -19.5(1) . . . . ?
O3 Cu1 O1 C1 -6.4(4) . . . . ?
O4 Cu1 O1 C1 -111.5(1) . . . . ?
N1 Cu1 O1 C1 83.3(1) . . . . ?
O1 Cu1 O2 C3 18.0(1) . . . . ?
O3 Cu1 O2 C3 -160.4(1) . . . . ?
O4 Cu1 O2 C3 108.0(1) . . . . ?
N1 Cu1 O2 C3 -71.4(1) . . . . ?
O1 Cu1 O3 C6 -83.9(4) . . . . ?
O2 Cu1 O3 C6 -70.7(1) . . . . ?
O4 Cu1 O3 C6 21.2(1) . . . . ?
N1 Cu1 O3 C6 -173.5(1) . . . . ?
O1 Cu1 O4 C8 156.2(1) . . . . ?
O2 Cu1 O4 C8 67.7(1) . . . . ?
O3 Cu1 O4 C8 -17.0(1) . . . . ?
N1 Cu1 O4 C8 -114.7(2) . . . . ?
O1 Cu1 N1 C11 135.0(1) . . . . ?
O1 Cu1 N1 C14 -101.6(1) . . . . ?
O2 Cu1 N1 C11 -136.5(1) . . . . ?
O2 Cu1 N1 C14 -13.1(1) . . . . ?
O3 Cu1 N1 C11 -52.0(1) . . . . ?
O3 Cu1 N1 C14 71.4(1) . . . . ?
O4 Cu1 N1 C11 45.9(2) . . . . ?
O4 Cu1 N1 C14 169.3(2) . . . . ?
Cu1 O1 C1 C2 15.2(2) . . . . ?
Cu1 O1 C1 C4 -164.01(9) . . . . ?
Cu1 O2 C3 C2 -11.4(2) . . . . ?
Cu1 O2 C3 C5 167.5(1) . . . . ?
Cu1 O3 C6 C7 -14.7(2) . . . . ?
Cu1 O3 C6 C9 169.0(1) . . . . ?
Cu1 O4 C8 C7 5.6(2) . . . . ?
Cu1 O4 C8 C10 -178.17(9) . . . . ?
Cu1 N1 C11 C12 162.3(1) . . . . ?
C14 N1 C11 C12 33.6(2) . . . . ?
Cu1 N1 C14 C13a -169.0(1) . . . . ?
Cu1 N1 C14 C13b -139.0(2) . . . . ?
C11 N1 C14 C13a -38.8(2) . . . . ?
C11 N1 C14 C13b -8.7(2) . . . . ?
O1 C1 C2 C3 0.3(3) . . . . ?
C4 C1 C2 C3 179.4(1) . . . . ?
O1 C1 C4 F1 -177.3(1) . . . . ?
80

O1 C1 C4 F2 62.7(2) . . . . ?
O1 C1 C4 F3 -55.8(2) . . . . ?
C2 C1 C4 F1 3.3(2) . . . . ?
C2 C1 C4 F2 -116.7(1) . . . . ?
C2 C1 C4 F3 124.9(1) . . . . ?
C1 C2 C3 O2 -1.0(3) . . . . ?
C1 C2 C3 C5 -179.9(2) . . . . ?
O2 C3 C5 F4 6.1(2) . . . . ?
O2 C3 C5 F5 127.2(2) . . . . ?
O2 C3 C5 F6 -113.5(2) . . . . ?
C2 C3 C5 F4 -174.8(1) . . . . ?
C2 C3 C5 F5 -53.8(2) . . . . ?
C2 C3 C5 F6 65.5(2) . . . . ?
O3 C6 C7 C8 -3.9(3) . . . . ?
C9 C6 C7 C8 172.3(1) . . . . ?
O3 C6 C9 F7 -31.0(2) . . . . ?
O3 C6 C9 F8 -151.2(1) . . . . ?
O3 C6 C9 F9 88.7(2) . . . . ?
C7 C6 C9 F7 152.2(1) . . . . ?
C7 C6 C9 F8 32.0(2) . . . . ?
C7 C6 C9 F9 -88.0(2) . . . . ?
C6 C7 C8 O4 8.9(2) . . . . ?
C6 C7 C8 C10 -167.1(1) . . . . ?
O4 C8 C10 F10 48.5(2) . . . . ?
O4 C8 C10 F11 -70.5(2) . . . . ?
O4 C8 C10 F12 168.9(1) . . . . ?
C7 C8 C10 F10 -134.9(1) . . . . ?
C7 C8 C10 F11 106.2(2) . . . . ?
C7 C8 C10 F12 -14.4(2) . . . . ?
N1 C11 C12 C13a -16.0(2) . . . . ?
N1 C11 C12 C13b -45.5(3) . . . . ?
C11 C12 C13a C13b -82.0(5) . . . . ?
C11 C12 C13a C14 -7.4(2) . . . . ?
C13b C12 C13a C14 74.6(5) . . . . ?
C11 C12 C13b C13a 104.8(4) . . . . ?
C11 C12 C13b C14 38.3(3) . . . . ?
C13a C12 C13b C14 -66.5(4) . . . . ?
C12 C13a C13b C14 109.1(2) . . . . ?
C14 C13a C13b C12 -109.1(2) . . . . ?
C12 C13a C14 N1 28.1(2) . . . . ?
C12 C13a C14 C13b -66.8(5) . . . . ?
C13b C13a C14 N1 94.8(5) . . . . ?
C12 C13b C14 N1 -19.3(4) . . . . ?
C12 C13b C14 C13a 74.1(4) . . . . ?
81

C13a C13b C14 N1 -93.4(4) . . . . ?

# End of CIF

82

Table A-2.CIF File For Cu(hfac)2(Me2NH)

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
bis(1,1,1,5,5,5-hexafluoropentanedionato)(dimethylamine)copper(II)
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety
?
_chemical_formula_sum
'C12 H8 Cu F12 N O4'
_chemical_formula_weight
521.73
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
Monoclinic
_symmetry_space_group_name_H-M P2(1)/n
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
_cell_length_a

10.6865(10)
83

_cell_length_b
8.9631(8)
_cell_length_c
19.6703(15)
_cell_angle_alpha
90.000(7)
_cell_angle_beta
100.674(7)
_cell_angle_gamma
90.00
_cell_volume
1851.5(3)
_cell_formula_units_Z
4
_cell_measurement_temperature 293(2)
_cell_measurement_reflns_used 25
_cell_measurement_theta_min
9.26
_cell_measurement_theta_max
11.3
_exptl_crystal_description
fragment
_exptl_crystal_colour
green
_exptl_crystal_size_max
0.15
_exptl_crystal_size_mid
0.45
_exptl_crystal_size_min
0.50
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.872
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
1024
_exptl_absorpt_coefficient_mu 1.316
_exptl_absorpt_correction_type '\h scans'
_exptl_absorpt_correction_T_min 0.2841
_exptl_absorpt_correction_T_max 0.3541
_exptl_absorpt_process_details ?
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
180
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device_type 'Enraf-Nonius CAD4 diffractometer'
_diffrn_measurement_method
'2-\w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
3
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time 3600
_diffrn_standards_decay_%
?
84

_diffrn_reflns_number
4358
_diffrn_reflns_av_R_equivalents 0.0284
_diffrn_reflns_av_sigmaI/netI 0.0341
_diffrn_reflns_limit_h_min
-13
_diffrn_reflns_limit_h_max
13
_diffrn_reflns_limit_k_min
-11
_diffrn_reflns_limit_k_max
0
_diffrn_reflns_limit_l_min
-25
_diffrn_reflns_limit_l_max
0
_diffrn_reflns_theta_min
2.37
_diffrn_reflns_theta_max
27.48
_reflns_number_total
4241
_reflns_number_gt
3055
_reflns_threshold_expression
>2sigma(I)
_computing_data_collection
'CAD4 Express (Enraf-Nonius, 1994)'
_computing_cell_refinement
'CAD4 Express (Enraf-Nonius, 1994)'
_computing_data_reduction
'XCAD4 (Harms & Wocaldo, 1996)'
_computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics 'Bruker SHELXTL'
_computing_publication_material 'Bruker SHELXTL'
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1529P)^2^+9.2726P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment mixed
_refine_ls_extinction_method
none
85

_refine_ls_extinction_coef
?
_refine_ls_number_reflns
4241
_refine_ls_number_parameters
356
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.0735
_refine_ls_R_factor_gt
0.0452
_refine_ls_wR_factor_ref
0.1716
_refine_ls_wR_factor_gt
0.1254
_refine_ls_goodness_of_fit_ref 0.622
_refine_ls_restrained_S_all
0.622
_refine_ls_shift/su_max
0.080
_refine_ls_shift/su_mean
0.006
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.16500(4) 0.06699(6) 0.98370(2) 0.03987(18) Uani 1 1 d . . .
F1 F -0.0265(3) 0.1028(5) 1.17542(15) 0.0759(10) Uani 1 1 d . . .
F2 F 0.1291(4) -0.0442(4) 1.20546(17) 0.0833(10) Uani 1 1 d . . .
F3 F 0.1376(3) 0.1798(4) 1.24424(13) 0.0691(9) Uani 1 1 d . . .
F4 F 0.5087(14) 0.348(2) 1.1729(7) 0.116(5) Uani 0.50 1 d P . .
F6 F 0.4066(15) 0.5096(14) 1.1161(12) 0.134(7) Uani 0.50 1 d P . .
F5 F 0.5238(18) 0.384(3) 1.0705(9) 0.140(10) Uani 0.50 1 d P . .
F4' F 0.4325(17) 0.471(2) 1.1538(10) 0.138(10) Uani 0.50 1 d P . .
F5' F 0.5466(9) 0.2916(15) 1.1353(11) 0.120(5) Uani 0.50 1 d P . .
F6' F 0.4830(18) 0.439(2) 1.0587(9) 0.119(8) Uani 0.50 1 d P . .
F7 F -0.1566(12) 0.3663(19) 0.8728(8) 0.085(5) Uani 0.52(3) 1 d P . .
F8 F -0.021(2) 0.525(2) 0.9085(19) 0.164(10) Uani 0.52(3) 1 d P . .
F9 F -0.0582(17) 0.459(4) 0.8038(12) 0.112(7) Uani 0.52(3) 1 d P . .
F9' F -0.1499(18) 0.367(2) 0.8498(18) 0.133(8) Uani 0.48(3) 1 d P . .
F8' F -0.008(3) 0.5235(19) 0.8323(12) 0.097(6) Uani 0.48(3) 1 d P . .
F7' F -0.0482(17) 0.5004(18) 0.9295(7) 0.086(4) Uani 0.48(3) 1 d P . .
F10 F 0.4115(10) 0.2384(12) 0.8152(6) 0.097(4) Uani 0.611(15) 1 d P . .
86

F11 F 0.2682(7) 0.144(2) 0.7410(3) 0.108(5) Uani 0.611(15) 1 d P . .

F12 F 0.3860(12) 0.0068(11) 0.8125(6) 0.100(5) Uani 0.611(15) 1 d P . .
F12' F 0.2615(17) 0.026(2) 0.7595(10) 0.115(7) Uani 0.389(15) 1 d P . .
F11' F 0.305(3) 0.248(2) 0.7578(12) 0.142(11) Uani 0.389(15) 1 d P . .
F10' F 0.4211(12) 0.104(5) 0.8258(8) 0.170(17) Uani 0.389(15) 1 d P . .
O1 O 0.3156(3) 0.2302(4) 1.02646(15) 0.0539(8) Uani 1 1 d . . .
O2 O 0.0992(3) 0.0824(3) 1.07027(13) 0.0434(6) Uani 1 1 d . . .
O3 O 0.2454(3) 0.0586(3) 0.90253(14) 0.0450(6) Uani 1 1 d . . .
O4 O 0.0469(3) 0.2246(3) 0.94271(14) 0.0439(6) Uani 1 1 d . . .
N1 N 0.2291(4) -0.1357(5) 1.0132(2) 0.0540(9) Uani 1 1 d . . .
H1N H 0.1863 -0.1627 1.0441 0.081 Uiso 1 1 calc R . .
C1 C 0.0985(4) 0.0968(6) 1.1887(2) 0.0494(10) Uani 1 1 d . . .
C2 C 0.1579(3) 0.1408(4) 1.12634(18) 0.0382(8) Uani 1 1 d . . .
C3 C 0.2637(4) 0.2296(5) 1.1386(2) 0.0432(9) Uani 1 1 d . . .
H3 H 0.2910 0.2652 1.1833 0.052 Uiso 1 1 calc R . .
C4 C 0.3335(4) 0.2704(5) 1.0874(2) 0.0415(8) Uani 1 1 d . . .
C5 C 0.4471(5) 0.3745(6) 1.1106(3) 0.0566(11) Uani 1 1 d . . .
C6 C -0.0422(5) 0.4185(6) 0.8713(3) 0.0623(13) Uani 1 1 d . . .
C7 C 0.0582(4) 0.2952(5) 0.8892(2) 0.0442(9) Uani 1 1 d . . .
C8 C 0.1451(4) 0.2732(5) 0.8457(2) 0.0520(10) Uani 1 1 d . . .
H8 H 0.1463 0.3389 0.8092 0.062 Uiso 1 1 calc R . .
C9 C 0.2302(4) 0.1545(5) 0.8557(2) 0.0453(9) Uani 1 1 d . . .
C10 C 0.3191(5) 0.1343(7) 0.8030(3) 0.0638(13) Uani 1 1 d . . .
C11 C 0.2076(5) -0.2508(6) 0.9611(3) 0.0667(13) Uani 1 1 d . . .
H11A H 0.2494 -0.2243 0.9237 0.100 Uiso 1 1 calc R . .
H11B H 0.1178 -0.2611 0.9441 0.100 Uiso 1 1 calc R . .
H11C H 0.2413 -0.3436 0.9810 0.100 Uiso 1 1 calc R . .
C12 C 0.3613(7) -0.1332(8) 1.0485(5) 0.121(3) Uani 1 1 d . . .
H12A H 0.3857 -0.2309 1.0661 0.182 Uiso 1 1 calc R . .
H12B H 0.3709 -0.0634 1.0861 0.182 Uiso 1 1 calc R . .
H12C H 0.4145 -0.1037 1.0165 0.182 Uiso 1 1 calc R . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0460(3) 0.0456(3) 0.0299(3) 0.00208(19) 0.01196(18) 0.0055(2)
F1 0.0485(15) 0.134(3) 0.0487(15) -0.0036(17) 0.0185(12) -0.0159(17)
F2 0.126(3) 0.069(2) 0.0628(19) 0.0251(16) 0.0391(19) 0.0039(19)
F3 0.0765(18) 0.100(2) 0.0347(12) -0.0134(14) 0.0215(12) -0.0276(17)
87

F4 0.081(8) 0.158(14) 0.091(7) 0.021(7) -0.033(6) -0.062(8)

F6 0.087(6) 0.047(4) 0.27(2) -0.030(9) 0.029(12) -0.012(4)
F5 0.095(9) 0.23(2) 0.120(14) -0.114(14) 0.088(10) -0.097(11)
F4' 0.139(16) 0.163(17) 0.146(12) -0.124(12) 0.115(13) -0.106(13)
F5' 0.049(5) 0.131(9) 0.167(14) -0.008(10) -0.013(7) -0.005(5)
F6' 0.137(15) 0.136(11) 0.084(7) 0.021(8) 0.018(8) -0.089(11)
F7 0.048(5) 0.105(9) 0.107(8) 0.052(7) 0.032(6) 0.023(5)
F8 0.138(12) 0.063(7) 0.24(2) -0.052(12) -0.098(13) 0.031(8)
F9 0.095(8) 0.147(15) 0.101(10) 0.082(11) 0.034(7) 0.048(8)
F9' 0.085(11) 0.079(9) 0.198(19) -0.031(11) -0.072(10) 0.013(7)
F8' 0.125(13) 0.078(8) 0.100(10) 0.048(7) 0.055(9) 0.038(7)
F7' 0.122(9) 0.075(8) 0.070(6) 0.007(5) 0.041(7) 0.053(7)
F10 0.076(6) 0.130(7) 0.096(8) -0.010(5) 0.047(6) -0.045(5)
F11 0.064(4) 0.233(15) 0.028(3) 0.001(6) 0.010(2) 0.030(7)
F12 0.119(11) 0.110(6) 0.092(8) 0.009(4) 0.073(8) 0.035(5)
F12' 0.135(13) 0.139(13) 0.091(11) -0.052(9) 0.075(10) -0.018(10)
F11' 0.20(2) 0.127(12) 0.138(19) 0.043(11) 0.14(2) 0.033(12)
F10' 0.030(6) 0.42(5) 0.059(7) 0.04(2) 0.014(5) 0.049(18)
O1 0.0588(18) 0.065(2) 0.0428(15) -0.0062(14) 0.0209(14) -0.0155(15)
O2 0.0456(14) 0.0563(17) 0.0296(12) -0.0003(12) 0.0106(11) -0.0032(12)
O3 0.0461(15) 0.0566(17) 0.0345(13) -0.0028(13) 0.0133(11) 0.0033(13)
O4 0.0495(15) 0.0457(15) 0.0387(14) 0.0058(12) 0.0139(11) 0.0053(12)
N1 0.060(2) 0.055(2) 0.048(2) 0.0045(18) 0.0124(17) 0.0069(18)
C1 0.050(2) 0.068(3) 0.0309(18) 0.0032(19) 0.0088(16) -0.007(2)
C2 0.0410(19) 0.045(2) 0.0295(16) 0.0026(15) 0.0092(14) 0.0030(16)
C3 0.0421(19) 0.052(2) 0.0360(19) -0.0044(17) 0.0099(15) -0.0009(17)
C4 0.0388(18) 0.043(2) 0.044(2) -0.0001(17) 0.0127(16) 0.0005(16)
C5 0.053(2) 0.062(3) 0.060(3) -0.008(2) 0.023(2) -0.011(2)
C6 0.067(3) 0.055(3) 0.064(3) 0.020(3) 0.012(3) 0.006(2)
C7 0.045(2) 0.046(2) 0.041(2) 0.0063(17) 0.0068(16) 0.0000(17)
C8 0.053(2) 0.062(3) 0.044(2) 0.015(2) 0.0145(18) -0.004(2)
C9 0.045(2) 0.060(2) 0.0329(18) -0.0056(18) 0.0116(16) -0.0110(19)
C10 0.061(3) 0.091(4) 0.045(2) 0.003(3) 0.022(2) -0.001(3)
C11 0.062(3) 0.052(3) 0.083(4) -0.006(3) 0.007(3) 0.006(2)
C12 0.104(5) 0.069(4) 0.155(7) -0.026(5) -0.066(5) 0.033(4)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
88

;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O3 1.950(3) . ?
Cu1 O2 1.964(3) . ?
Cu1 O4 1.965(3) . ?
Cu1 N1 1.989(4) . ?
Cu1 O1 2.222(3) . ?
F1 C1 1.314(5) . ?
F2 C1 1.332(6) . ?
F3 C1 1.324(5) . ?
F4 F5' 1.038(16) . ?
F4 C5 1.301(11) . ?
F4 F4' 1.38(2) . ?
F6 F4' 0.82(2) . ?
F6 C5 1.298(13) . ?
F6 F6' 1.64(2) . ?
F5 F6' 0.67(3) . ?
F5 C5 1.241(11) . ?
F5 F5' 1.50(2) . ?
F4' C5 1.241(11) . ?
F5' C5 1.314(12) . ?
F6' C5 1.291(14) . ?
F7 C6 1.313(13) . ?
F8 F7' 0.59(5) . ?
F8 C6 1.199(17) . ?
F8 F8' 1.53(3) . ?
F9 F8' 0.911(16) . ?
F9 C6 1.358(17) . ?
F9 F9' 1.67(3) . ?
F9' C6 1.240(17) . ?
F8' C6 1.311(14) . ?
F7' C6 1.371(14) . ?
F10 F10' 1.22(3) . ?
F10 C10 1.348(9) . ?
F10 F11' 1.45(3) . ?
F11 F11' 1.047(19) . ?
F11 F12' 1.119(17) . ?
F11 C10 1.243(8) . ?
89

F12 F10' 0.97(4) . ?

F12 C10 1.343(11) . ?
F12 F12' 1.54(2) . ?
F12' C10 1.360(14) . ?
F11' C10 1.344(15) . ?
F10' C10 1.132(13) . ?
O1 C4 1.232(5) . ?
O2 C2 1.276(5) . ?
O3 C9 1.248(5) . ?
O4 C7 1.253(5) . ?
N1 C11 1.442(6) . ?
N1 C12 1.454(7) . ?
C1 C2 1.534(5) . ?
C2 C3 1.367(6) . ?
C3 C4 1.408(5) . ?
C4 C5 1.532(6) . ?
C6 C7 1.535(6) . ?
C7 C8 1.389(6) . ?
C8 C9 1.390(6) . ?
C9 C10 1.541(6) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 Cu1 O2 174.65(12) . . ?
O3 Cu1 O4 92.22(12) . . ?
O2 Cu1 O4 89.96(12) . . ?
O3 Cu1 N1 91.36(14) . . ?
O2 Cu1 N1 88.30(14) . . ?
O4 Cu1 N1 159.42(15) . . ?
O3 Cu1 O1 86.39(12) . . ?
O2 Cu1 O1 88.63(11) . . ?
O4 Cu1 O1 92.70(14) . . ?
N1 Cu1 O1 107.75(15) . . ?
F5' F4 C5 67.3(10) . . ?
F5' F4 F4' 119.0(15) . . ?
C5 F4 F4' 55.1(7) . . ?
F4' F6 C5 67.5(14) . . ?
F4' F6 F6' 109.3(19) . . ?
90

C5 F6 F6' 50.5(8) . . ?
F6' F5 C5 78.8(19) . . ?
F6' F5 F5' 134(2) . . ?
C5 F5 F5' 56.3(8) . . ?
F6 F4' C5 74.9(13) . . ?
F6 F4' F4 132.0(17) . . ?
C5 F4' F4 59.3(8) . . ?
F4 F5' C5 65.9(10) . . ?
F4 F5' F5 108.3(15) . . ?
C5 F5' F5 51.8(7) . . ?
F5 F6' C5 70.5(18) . . ?
F5 F6' F6 115(2) . . ?
C5 F6' F6 50.9(8) . . ?
F7' F8 C6 94(3) . . ?
F7' F8 F8' 146(4) . . ?
C6 F8 F8' 55.8(11) . . ?
F8' F9 C6 67.3(17) . . ?
F8' F9 F9' 109(3) . . ?
C6 F9 F9' 46.9(8) . . ?
C6 F9' F9 53.1(9) . . ?
F9 F8' C6 72.9(17) . . ?
F9 F8' F8 117(3) . . ?
C6 F8' F8 49.2(8) . . ?
F8 F7' C6 61(2) . . ?
F10' F10 C10 52.0(8) . . ?
F10' F10 F11' 102.8(12) . . ?
C10 F10 F11' 57.3(8) . . ?
F11' F11 F12' 141.4(15) . . ?
F11' F11 C10 71.3(11) . . ?
F12' F11 C10 70.1(9) . . ?
F10' F12 C10 55.9(11) . . ?
F10' F12 F12' 108.9(15) . . ?
C10 F12 F12' 55.8(7) . . ?
F11 F12' C10 59.2(8) . . ?
F11 F12' F12 103.2(12) . . ?
C10 F12' F12 54.8(8) . . ?
F11 F11' C10 61.2(9) . . ?
F11 F11' F10 112.7(15) . . ?
C10 F11' F10 57.5(9) . . ?
F12 F10' C10 79.2(16) . . ?
F12 F10' F10 145.7(17) . . ?
C10 F10' F10 69.6(16) . . ?
C4 O1 Cu1 122.2(3) . . ?
C2 O2 Cu1 125.5(2) . . ?
91

C9 O3 Cu1 124.1(3) . . ?
C7 O4 Cu1 123.6(3) . . ?
C11 N1 C12 111.2(4) . . ?
C11 N1 Cu1 116.4(3) . . ?
C12 N1 Cu1 112.1(4) . . ?
F1 C1 F3 107.2(4) . . ?
F1 C1 F2 106.4(4) . . ?
F3 C1 F2 107.7(4) . . ?
F1 C1 C2 112.7(3) . . ?
F3 C1 C2 113.6(4) . . ?
F2 C1 C2 108.8(4) . . ?
O2 C2 C3 130.5(3) . . ?
O2 C2 C1 112.1(3) . . ?
C3 C2 C1 117.4(3) . . ?
C2 C3 C4 123.8(4) . . ?
O1 C4 C3 127.7(4) . . ?
O1 C4 C5 116.1(4) . . ?
C3 C4 C5 116.2(4) . . ?
F4' C5 F5 124.8(11) . . ?
F4' C5 F6' 109.0(12) . . ?
F5 C5 F6' 30.7(15) . . ?
F4' C5 F4 65.6(10) . . ?
F5 C5 F4 109.4(11) . . ?
F6' C5 F4 130.9(10) . . ?
F4' C5 F6 37.6(11) . . ?
F5 C5 F6 105.1(13) . . ?
F6' C5 F6 78.6(12) . . ?
F4 C5 F6 102.1(11) . . ?
F4' C5 F5' 109.6(12) . . ?
F5 C5 F5' 71.9(12) . . ?
F6' C5 F5' 101.9(11) . . ?
F4 C5 F5' 46.8(8) . . ?
F6 C5 F5' 139.1(10) . . ?
F4' C5 C4 115.7(7) . . ?
F5 C5 C4 115.6(8) . . ?
F6' C5 C4 111.8(9) . . ?
F4 C5 C4 113.8(6) . . ?
F6 C5 C4 109.6(8) . . ?
F5' C5 C4 107.9(7) . . ?
F8 C6 F9' 124.5(14) . . ?
F8 C6 F8' 75.0(16) . . ?
F9' C6 F8' 114.5(13) . . ?
F8 C6 F7 110.1(19) . . ?
F9' C6 F7 20.9(18) . . ?
92

F8' C6 F7 129.3(14) . . ?
F8 C6 F9 110.9(12) . . ?
F9' C6 F9 80.0(13) . . ?
F8' C6 F9 39.9(7) . . ?
F7 C6 F9 99.7(11) . . ?
F8 C6 F7' 25(2) . . ?
F9' C6 F7' 107.6(17) . . ?
F8' C6 F7' 99.5(12) . . ?
F7 C6 F7' 89.2(11) . . ?
F9 C6 F7' 131.0(15) . . ?
F8 C6 C7 112.9(8) . . ?
F9' C6 C7 111.9(10) . . ?
F8' C6 C7 112.9(10) . . ?
F7 C6 C7 110.6(8) . . ?
F9 C6 C7 111.9(10) . . ?
F7' C6 C7 109.5(8) . . ?
O4 C7 C8 128.7(4) . . ?
O4 C7 C6 112.6(4) . . ?
C8 C7 C6 118.7(4) . . ?
C7 C8 C9 121.0(4) . . ?
O3 C9 C8 128.6(4) . . ?
O3 C9 C10 113.8(4) . . ?
C8 C9 C10 117.5(4) . . ?
F10' C10 F11 128.2(9) . . ?
F10' C10 F12 45(2) . . ?
F11 C10 F12 108.6(9) . . ?
F10' C10 F11' 115.3(16) . . ?
F11 C10 F11' 47.5(9) . . ?
F12 C10 F11' 137.0(8) . . ?
F10' C10 F10 58.4(19) . . ?
F11 C10 F10 107.5(9) . . ?
F12 C10 F10 102.2(7) . . ?
F11' C10 F10 65.2(12) . . ?
F10' C10 F12' 111.6(19) . . ?
F11 C10 F12' 50.7(8) . . ?
F12 C10 F12' 69.5(11) . . ?
F11' C10 F12' 98.2(12) . . ?
F10 C10 F12' 146.7(8) . . ?
F10' C10 C9 115.4(8) . . ?
F11 C10 C9 116.2(5) . . ?
F12 C10 C9 112.7(6) . . ?
F11' C10 C9 110.3(7) . . ?
F10 C10 C9 108.7(6) . . ?
F12' C10 C9 104.1(6) . . ?
93

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
F6' F6 F4' C5 -28.9(14) . . . . ?
C5 F6 F4' F4 17(2) . . . . ?
F6' F6 F4' F4 -11(4) . . . . ?
F5' F4 F4' F6 3(4) . . . . ?
C5 F4 F4' F6 -20(3) . . . . ?
F5' F4 F4' C5 22.6(13) . . . . ?
F4' F4 F5' C5 -20.0(11) . . . . ?
C5 F4 F5' F5 30.6(9) . . . . ?
F4' F4 F5' F5 10.6(18) . . . . ?
F6' F5 F5' F4 -20(5) . . . . ?
C5 F5 F5' F4 -36.3(11) . . . . ?
F6' F5 F5' C5 16(4) . . . . ?
F5' F5 F6' C5 -13(3) . . . . ?
C5 F5 F6' F6 26(2) . . . . ?
F5' F5 F6' F6 12(5) . . . . ?
F4' F6 F6' F5 4(4) . . . . ?
C5 F6 F6' F5 -32(3) . . . . ?
F4' F6 F6' C5 35.4(19) . . . . ?
F8' F9 F9' C6 -29(2) . . . . ?
F9' F9 F8' C6 22.5(15) . . . . ?
C6 F9 F8' F8 -22.0(18) . . . . ?
F9' F9 F8' F8 0(3) . . . . ?
F7' F8 F8' F9 -2(7) . . . . ?
C6 F8 F8' F9 28(2) . . . . ?
F7' F8 F8' C6 -30(6) . . . . ?
F8' F8 F7' C6 25(5) . . . . ?
F11' F11 F12' C10 2(2) . . . . ?
F11' F11 F12' F12 -32(2) . . . . ?
C10 F11 F12' F12 -33.9(7) . . . . ?
F10' F12 F12' F11 17.6(18) . . . . ?
C10 F12 F12' F11 36.0(8) . . . . ?
F10' F12 F12' C10 -18.4(14) . . . . ?
F12' F11 F11' C10 -2(2) . . . . ?
94

F12' F11 F11' F10 25(3) . . . . ?

C10 F11 F11' F10 26.6(9) . . . . ?
F10' F10 F11' F11 -1.4(15) . . . . ?
C10 F10 F11' F11 -27.7(10) . . . . ?
F10' F10 F11' C10 26.2(9) . . . . ?
F12' F12 F10' C10 18.3(13) . . . . ?
C10 F12 F10' F10 -25(3) . . . . ?
F12' F12 F10' F10 -6(4) . . . . ?
C10 F10 F10' F12 26(3) . . . . ?
F11' F10 F10' F12 -2(3) . . . . ?
F11' F10 F10' C10 -28.2(10) . . . . ?
O3 Cu1 O1 C4 -168.7(4) . . . . ?
O2 Cu1 O1 C4 9.4(3) . . . . ?
O4 Cu1 O1 C4 99.3(3) . . . . ?
N1 Cu1 O1 C4 -78.4(4) . . . . ?
O3 Cu1 O2 C2 7.3(15) . . . . ?
O4 Cu1 O2 C2 -106.8(3) . . . . ?
N1 Cu1 O2 C2 93.7(3) . . . . ?
O1 Cu1 O2 C2 -14.1(3) . . . . ?
O2 Cu1 O3 C9 -100.8(13) . . . . ?
O4 Cu1 O3 C9 13.2(3) . . . . ?
N1 Cu1 O3 C9 172.9(3) . . . . ?
O1 Cu1 O3 C9 -79.4(3) . . . . ?
O3 Cu1 O4 C7 -11.6(3) . . . . ?
O2 Cu1 O4 C7 163.5(3) . . . . ?
N1 Cu1 O4 C7 -111.4(5) . . . . ?
O1 Cu1 O4 C7 74.9(3) . . . . ?
O3 Cu1 N1 C11 -49.3(4) . . . . ?
O2 Cu1 N1 C11 136.0(4) . . . . ?
O4 Cu1 N1 C11 50.7(6) . . . . ?
O1 Cu1 N1 C11 -136.0(3) . . . . ?
O3 Cu1 N1 C12 80.4(5) . . . . ?
O2 Cu1 N1 C12 -94.3(5) . . . . ?
O4 Cu1 N1 C12 -179.6(5) . . . . ?
O1 Cu1 N1 C12 -6.2(5) . . . . ?
Cu1 O2 C2 C3 14.0(6) . . . . ?
Cu1 O2 C2 C1 -163.9(3) . . . . ?
F1 C1 C2 O2 -43.6(5) . . . . ?
F3 C1 C2 O2 -165.8(4) . . . . ?
F2 C1 C2 O2 74.2(5) . . . . ?
F1 C1 C2 C3 138.2(4) . . . . ?
F3 C1 C2 C3 16.0(6) . . . . ?
F2 C1 C2 C3 -104.0(5) . . . . ?
O2 C2 C3 C4 -2.5(7) . . . . ?
95

C1 C2 C3 C4 175.4(4) . . . . ?
Cu1 O1 C4 C3 -2.9(6) . . . . ?
Cu1 O1 C4 C5 175.6(3) . . . . ?
C2 C3 C4 O1 -3.1(7) . . . . ?
C2 C3 C4 C5 178.3(4) . . . . ?
F6 F4' C5 F5 68(3) . . . . ?
F4 F4' C5 F5 -97.4(16) . . . . ?
F6 F4' C5 F6' 38(2) . . . . ?
F4 F4' C5 F6' -127.1(11) . . . . ?
F6 F4' C5 F4 165(2) . . . . ?
F4 F4' C5 F6 -165(2) . . . . ?
F6 F4' C5 F5' 148.6(18) . . . . ?
F4 F4' C5 F5' -16.4(10) . . . . ?
F6 F4' C5 C4 -89.1(18) . . . . ?
F4 F4' C5 C4 105.9(8) . . . . ?
F6' F5 C5 F4' -67(3) . . . . ?
F5' F5 C5 F4' 101.6(16) . . . . ?
F5' F5 C5 F6' 168(3) . . . . ?
F6' F5 C5 F4 -140(3) . . . . ?
F5' F5 C5 F4 28.4(11) . . . . ?
F6' F5 C5 F6 -31(3) . . . . ?
F5' F5 C5 F6 137.4(11) . . . . ?
F6' F5 C5 F5' -168(3) . . . . ?
F6' F5 C5 C4 90(3) . . . . ?
F5' F5 C5 C4 -101.7(9) . . . . ?
F5 F6' C5 F4' 127(3) . . . . ?
F6 F6' C5 F4' -22.5(15) . . . . ?
F6 F6' C5 F5 -150(3) . . . . ?
F5 F6' C5 F4 53(3) . . . . ?
F6 F6' C5 F4 -96.2(16) . . . . ?
F5 F6' C5 F6 150(3) . . . . ?
F5 F6' C5 F5' 11(3) . . . . ?
F6 F6' C5 F5' -138.2(10) . . . . ?
F5 F6' C5 C4 -104(3) . . . . ?
F6 F6' C5 C4 106.7(10) . . . . ?
F5' F4 C5 F4' -158.6(13) . . . . ?
F5' F4 C5 F5 -38.3(15) . . . . ?
F4' F4 C5 F5 120.3(12) . . . . ?
F5' F4 C5 F6' -64.0(19) . . . . ?
F4' F4 C5 F6' 94.6(16) . . . . ?
F5' F4 C5 F6 -149.3(12) . . . . ?
F4' F4 C5 F6 9.3(12) . . . . ?
F4' F4 C5 F5' 158.6(13) . . . . ?
F5' F4 C5 C4 92.7(11) . . . . ?
96

F4' F4 C5 C4 -108.7(8) . . . . ?
F6' F6 C5 F4' 144(2) . . . . ?
F4' F6 C5 F5 -128.2(19) . . . . ?
F6' F6 C5 F5 15.5(16) . . . . ?
F4' F6 C5 F6' -144(2) . . . . ?
F4' F6 C5 F4 -14.0(19) . . . . ?
F6' F6 C5 F4 129.7(10) . . . . ?
F4' F6 C5 F5' -49(3) . . . . ?
F6' F6 C5 F5' 95.1(16) . . . . ?
F4' F6 C5 C4 107.0(18) . . . . ?
F6' F6 C5 C4 -109.3(10) . . . . ?
F4 F5' C5 F4' 20.6(13) . . . . ?
F5 F5' C5 F4' -121.4(11) . . . . ?
F4 F5' C5 F5 142.0(14) . . . . ?
F4 F5' C5 F6' 136.0(13) . . . . ?
F5 F5' C5 F6' -6.0(16) . . . . ?
F5 F5' C5 F4 -142.0(14) . . . . ?
F4 F5' C5 F6 50(2) . . . . ?
F5 F5' C5 F6 -92.4(17) . . . . ?
F4 F5' C5 C4 -106.1(10) . . . . ?
F5 F5' C5 C4 111.8(9) . . . . ?
O1 C4 C5 F4' 145.0(15) . . . . ?
C3 C4 C5 F4' -36.3(15) . . . . ?
O1 C4 C5 F5 -13.9(17) . . . . ?
C3 C4 C5 F5 164.8(16) . . . . ?
O1 C4 C5 F6' 19.4(12) . . . . ?
C3 C4 C5 F6' -161.9(11) . . . . ?
O1 C4 C5 F4 -141.8(13) . . . . ?
C3 C4 C5 F4 36.9(14) . . . . ?
O1 C4 C5 F6 104.6(12) . . . . ?
C3 C4 C5 F6 -76.7(12) . . . . ?
O1 C4 C5 F5' -91.9(11) . . . . ?
C3 C4 C5 F5' 86.8(11) . . . . ?
F7' F8 C6 F9' 54(3) . . . . ?
F8' F8 C6 F9' -109.7(18) . . . . ?
F7' F8 C6 F8' 164(3) . . . . ?
F7' F8 C6 F7 37(3) . . . . ?
F8' F8 C6 F7 -126.9(18) . . . . ?
F7' F8 C6 F9 146(3) . . . . ?
F8' F8 C6 F9 -17.6(18) . . . . ?
F8' F8 C6 F7' -164(3) . . . . ?
F7' F8 C6 C7 -87(3) . . . . ?
F8' F8 C6 C7 108.9(9) . . . . ?
F9 F9' C6 F8 108.6(16) . . . . ?
97

F9 F9' C6 F8' 20.4(17) . . . . ?

F9 F9' C6 F7 160(4) . . . . ?
F9 F9' C6 F7' 130.0(16) . . . . ?
F9 F9' C6 C7 -109.7(10) . . . . ?
F9 F8' C6 F8 -154(3) . . . . ?
F9 F8' C6 F9' -32(3) . . . . ?
F8 F8' C6 F9' 121.5(14) . . . . ?
F9 F8' C6 F7 -50(2) . . . . ?
F8 F8' C6 F7 103.9(19) . . . . ?
F8 F8' C6 F9 154(3) . . . . ?
F9 F8' C6 F7' -146.8(19) . . . . ?
F8 F8' C6 F7' 7.1(17) . . . . ?
F9 F8' C6 C7 97(2) . . . . ?
F8 F8' C6 C7 -108.9(10) . . . . ?
F8' F9 C6 F8 27(3) . . . . ?
F9' F9 C6 F8 -123.2(15) . . . . ?
F8' F9 C6 F9' 150(3) . . . . ?
F9' F9 C6 F8' -150(3) . . . . ?
F8' F9 C6 F7 143(2) . . . . ?
F9' F9 C6 F7 -7.3(17) . . . . ?
F8' F9 C6 F7' 46(2) . . . . ?
F9' F9 C6 F7' -104.6(18) . . . . ?
F8' F9 C6 C7 -100(2) . . . . ?
F9' F9 C6 C7 109.7(10) . . . . ?
F8 F7' C6 F9' -136(3) . . . . ?
F8 F7' C6 F8' -16(3) . . . . ?
F8 F7' C6 F7 -146(3) . . . . ?
F8 F7' C6 F9 -44(4) . . . . ?
F8 F7' C6 C7 102(3) . . . . ?
Cu1 O4 C7 C8 5.2(7) . . . . ?
Cu1 O4 C7 C6 -176.4(3) . . . . ?
F8 C6 C7 O4 75(3) . . . . ?
F9' C6 C7 O4 -71(2) . . . . ?
F8' C6 C7 O4 157.7(16) . . . . ?
F7 C6 C7 O4 -48.9(10) . . . . ?
F9 C6 C7 O4 -159.0(16) . . . . ?
F7' C6 C7 O4 47.8(9) . . . . ?
F8 C6 C7 C8 -106(3) . . . . ?
F9' C6 C7 C8 107(2) . . . . ?
F8' C6 C7 C8 -23.8(17) . . . . ?
F7 C6 C7 C8 129.7(9) . . . . ?
F9 C6 C7 C8 19.5(17) . . . . ?
F7' C6 C7 C8 -133.6(9) . . . . ?
O4 C7 C8 C9 4.4(8) . . . . ?
98

C6 C7 C8 C9 -173.9(4) . . . . ?
Cu1 O3 C9 C8 -8.7(6) . . . . ?
Cu1 O3 C9 C10 171.6(3) . . . . ?
C7 C8 C9 O3 -2.5(7) . . . . ?
C7 C8 C9 C10 177.3(4) . . . . ?
F12 F10' C10 F11 -78(2) . . . . ?
F10 F10' C10 F11 88(2) . . . . ?
F10 F10' C10 F12 165.5(17) . . . . ?
F12 F10' C10 F11' -132.2(15) . . . . ?
F10 F10' C10 F11' 33.3(14) . . . . ?
F12 F10' C10 F10 -165.5(17) . . . . ?
F12 F10' C10 F12' -21.3(17) . . . . ?
F10 F10' C10 F12' 144.2(11) . . . . ?
F12 F10' C10 C9 97.3(16) . . . . ?
F10 F10' C10 C9 -97.2(11) . . . . ?
F11' F11 C10 F10' -91(3) . . . . ?
F12' F11 C10 F10' 88(3) . . . . ?
F11' F11 C10 F12 -137.6(12) . . . . ?
F12' F11 C10 F12 41.1(10) . . . . ?
F12' F11 C10 F11' 178.7(14) . . . . ?
F11' F11 C10 F10 -27.7(13) . . . . ?
F12' F11 C10 F10 150.9(10) . . . . ?
F11' F11 C10 F12' -178.7(14) . . . . ?
F11' F11 C10 C9 94.3(11) . . . . ?
F12' F11 C10 C9 -87.1(10) . . . . ?
F12' F12 C10 F10' -158.9(17) . . . . ?
F10' F12 C10 F11 126.0(15) . . . . ?
F12' F12 C10 F11 -32.9(8) . . . . ?
F10' F12 C10 F11' 79(2) . . . . ?
F12' F12 C10 F11' -80(2) . . . . ?
F10' F12 C10 F10 12.6(14) . . . . ?
F12' F12 C10 F10 -146.3(9) . . . . ?
F10' F12 C10 F12' 158.9(17) . . . . ?
F10' F12 C10 C9 -103.9(14) . . . . ?
F12' F12 C10 C9 97.2(8) . . . . ?
F11 F11' C10 F10' 119.7(18) . . . . ?
F10 F11' C10 F10' -31.0(17) . . . . ?
F10 F11' C10 F11 -150.7(12) . . . . ?
F11 F11' C10 F12 70(2) . . . . ?
F10 F11' C10 F12 -81.1(18) . . . . ?
F11 F11' C10 F10 150.7(12) . . . . ?
F11 F11' C10 F12' 1.0(11) . . . . ?
F10 F11' C10 F12' -149.7(9) . . . . ?
F11 F11' C10 C9 -107.4(9) . . . . ?
99

F10 F11' C10 C9 101.9(8) . . . . ?

F11' F10 C10 F10' 146.8(13) . . . . ?
F10' F10 C10 F11 -124.6(12) . . . . ?
F11' F10 C10 F11 22.2(9) . . . . ?
F10' F10 C10 F12 -10.4(13) . . . . ?
F11' F10 C10 F12 136.4(9) . . . . ?
F10' F10 C10 F11' -146.8(13) . . . . ?
F10' F10 C10 F12' -81(2) . . . . ?
F11' F10 C10 F12' 65(2) . . . . ?
F10' F10 C10 C9 108.9(11) . . . . ?
F11' F10 C10 C9 -104.3(8) . . . . ?
F11 F12' C10 F10' -122.4(14) . . . . ?
F12 F12' C10 F10' 15.9(14) . . . . ?
F12 F12' C10 F11 138.3(9) . . . . ?
F11 F12' C10 F12 -138.3(9) . . . . ?
F11 F12' C10 F11' -1.0(10) . . . . ?
F12 F12' C10 F11' 137.3(9) . . . . ?
F11 F12' C10 F10 -58(2) . . . . ?
F12 F12' C10 F10 81(2) . . . . ?
F11 F12' C10 C9 112.5(7) . . . . ?
F12 F12' C10 C9 -109.3(7) . . . . ?
O3 C9 C10 F10' -42(3) . . . . ?
C8 C9 C10 F10' 138(3) . . . . ?
O3 C9 C10 F11 133.6(12) . . . . ?
C8 C9 C10 F11 -46.2(13) . . . . ?
O3 C9 C10 F12 7.5(9) . . . . ?
C8 C9 C10 F12 -172.3(7) . . . . ?
O3 C9 C10 F11' -174.8(15) . . . . ?
C8 C9 C10 F11' 5.5(16) . . . . ?
O3 C9 C10 F10 -105.0(8) . . . . ?
C8 C9 C10 F10 75.2(8) . . . . ?
O3 C9 C10 F12' 80.8(13) . . . . ?
C8 C9 C10 F12' -99.0(13) . . . . ?
_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full
27.48
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max 0.475
_refine_diff_density_min -0.391
_refine_diff_density_rms 0.074

100

Table A-3. CIF File For (Et3NH)[Cu(hfac)3]

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
triethylammonium tris(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)cuprate(II)
;
_chemical_name_common
(Et3NH)[Cu(acac)3]
_chemical_melting_point
?
_chemical_formula_moiety
'C6 H16 N1 1+, C15 H3 Cu O6 F18 1-'
_chemical_formula_sum
'C21 H19 Cu F18 N O6'
_chemical_formula_weight
786,91
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
monoclinic
_symmetry_space_group_name_H-M P21/n
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
_cell_length_a
_cell_length_b

12.439(4)
18.078(6)
101

_cell_length_c
12.896(4)
_cell_angle_alpha
90
_cell_angle_beta
98.383(17)
_cell_angle_gamma
90
_cell_volume
2869.0(16)
_cell_formula_units_Z
4
_cell_measurement_temperature 100
_cell_measurement_reflns_used 20572
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
30.0
_exptl_crystal_description
needle
_exptl_crystal_colour
yellow
_exptl_crystal_size_max
0.27
_exptl_crystal_size_mid
0.07
_exptl_crystal_size_min
0.08
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.822
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
1564
_exptl_absorpt_coefficient_mu 0.917
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.781
_exptl_absorpt_correction_T_max 0.937
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
100
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
_diffrn_reflns_number
7941
102

_diffrn_reflns_av_R_equivalents 0.036
_diffrn_reflns_av_sigmaI/netI 0.0776
_diffrn_reflns_limit_h_min
0
_diffrn_reflns_limit_h_max
17
_diffrn_reflns_limit_k_min
0
_diffrn_reflns_limit_k_max
25
_diffrn_reflns_limit_l_min
-18
_diffrn_reflns_limit_l_max
17
_diffrn_reflns_theta_min
2.13
_diffrn_reflns_theta_max
30.04
_reflns_number_total
7941
_reflns_number_gt
5519
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0733P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment mixed
_refine_ls_extinction_method
SHELXL
_refine_ls_extinction_coef
0.0310(15)
103

_refine_ls_extinction_expression
'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^'
_refine_ls_number_reflns
7941
_refine_ls_number_parameters
420
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.1046
_refine_ls_R_factor_gt
0.0628
_refine_ls_wR_factor_ref
0.1533
_refine_ls_wR_factor_gt
0.1337
_refine_ls_goodness_of_fit_ref 1.165
_refine_ls_restrained_S_all
1.165
_refine_ls_shift/su_max
0.006
_refine_ls_shift/su_mean
0.001
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.09017(3) 0.22398(2) 0.46468(3) 0.01021(12) Uani 1 1 d . . .
F1 F 0.16299(18) 0.41959(13) 0.20175(15) 0.0299(5) Uani 1 1 d . . .
F2 F -0.01041(18) 0.42692(12) 0.19097(15) 0.0298(5) Uani 1 1 d . . .
F3 F 0.06294(16) 0.32860(11) 0.13876(13) 0.0212(4) Uani 1 1 d . . .
F4 F 0.12860(17) 0.50609(10) 0.55438(15) 0.0254(4) Uani 1 1 d . . .
F5 F 0.22218(17) 0.42461(12) 0.65076(16) 0.0287(5) Uani 1 1 d . . .
F6 F 0.05187(18) 0.43755(12) 0.65848(16) 0.0283(5) Uani 1 1 d . . .
F7 F 0.49742(16) 0.29337(12) 0.49404(16) 0.0270(5) Uani 1 1 d . . .
F8 F 0.47047(16) 0.34238(12) 0.64001(15) 0.0281(5) Uani 1 1 d . . .
F9 F 0.38463(16) 0.38316(11) 0.49470(17) 0.0279(5) Uani 1 1 d . . .
F10 F 0.33223(16) 0.15858(12) 0.82894(15) 0.0266(5) Uani 1 1 d . . .
F11 F 0.24689(19) 0.06997(12) 0.74132(18) 0.0347(5) Uani 1 1 d . . .
F12 F 0.15781(17) 0.15335(14) 0.81134(16) 0.0343(5) Uani 1 1 d . . .
F13 F 0.09804(19) 0.02162(13) 0.23428(18) 0.0358(5) Uani 1 1 d . . .
F14 F -0.0050(2) -0.04322(15) 0.3195(3) 0.0692(11) Uani 1 1 d . . .
F15 F 0.15536(19) -0.01409(12) 0.39069(19) 0.0365(6) Uani 1 1 d . . .
104

F16 F -0.29989(17) 0.17903(15) 0.33125(18) 0.0382(6) Uani 1 1 d . . .

F17 F -0.28595(17) 0.18406(18) 0.49726(19) 0.0502(8) Uani 1 1 d . . .
F18 F -0.29622(18) 0.07948(14) 0.4188(2) 0.0473(7) Uani 1 1 d . . .
O1 O 0.06636(16) 0.27998(12) 0.32753(16) 0.0137(4) Uani 1 1 d . . .
O2 O 0.08590(17) 0.31524(11) 0.54527(15) 0.0130(4) Uani 1 1 d . . .
O3 O 0.27217(16) 0.25424(12) 0.46141(15) 0.0137(4) Uani 1 1 d . . .
O4 O 0.14790(17) 0.17062(12) 0.59739(16) 0.0149(4) Uani 1 1 d . . .
O5 O 0.10000(16) 0.13116(11) 0.38901(15) 0.0126(4) Uani 1 1 d . . .
O6 O -0.08379(18) 0.20478(13) 0.46239(17) 0.0174(5) Uani 1 1 d . . .
N1 N 0.3282(2) 0.17666(15) 0.2790(2) 0.0137(5) Uani 1 1 d . . .
H1 H 0.303(3) 0.196(2) 0.329(3) 0.016(9) Uiso 1 1 d . . .
C1 C 0.0805(2) 0.34791(17) 0.3228(2) 0.0130(6) Uani 1 1 d . . .
C2 C 0.10069(12) 0.39900(9) 0.40512(11) 0.0150(6) Uani 1 1 d . . .
H2 H 0.1149 0.4494 0.3881 0.019 Uiso 1 1 d R . .
C3 C 0.10116(12) 0.37849(9) 0.50850(11) 0.0121(5) Uani 1 1 d R . .
C4 C 0.07395(12) 0.38052(9) 0.21248(11) 0.0164(6) Uani 1 1 d R . .
C5 C 0.12630(12) 0.43775(9) 0.59351(11) 0.0157(6) Uani 1 1 d R . .
H7 H 0.3688 0.2490 0.7049 0.020 Uiso 1 1 d R . .
C6 C 0.3279(2) 0.26659(16) 0.5489(2) 0.0128(6) Uani 1 1 d . . .
C7 C 0.3172(2) 0.23493(17) 0.6455(2) 0.0132(6) Uani 1 1 d . . .
C8 C 0.2336(2) 0.18599(17) 0.6592(2) 0.0140(6) Uani 1 1 d . . .
H12 H -0.1240 0.0414 0.3652 0.018 Uiso 1 1 d R . .
C9 C 0.4208(2) 0.32240(18) 0.5461(2) 0.0160(6) Uani 1 1 d . . .
C10 C 0.2430(3) 0.14184(19) 0.7617(2) 0.0199(7) Uani 1 1 d . . .
H16A H 0.4804 0.2184 0.3226 0.026 Uiso 1 1 d R . .
H16B H 0.4561 0.1998 0.2027 0.026 Uiso 1 1 d R . .
C11 C 0.0261(2) 0.08260(17) 0.3718(2) 0.0155(6) Uani 1 1 d . . .
H17A H 0.4641 0.3278 0.2248 0.020 Uiso 1 1 d R . .
H17B H 0.3708 0.3233 0.2943 0.020 Uiso 1 1 d R . .
H17C H 0.3466 0.3047 0.1744 0.020 Uiso 1 1 d R . .
C12 C -0.0816(3) 0.08489(19) 0.3845(3) 0.0196(7) Uani 1 1 d . . .
H18A H 0.1760 0.1507 0.2036 0.026 Uiso 1 1 d R . .
H18B H 0.2179 0.2271 0.1678 0.026 Uiso 1 1 d R . .
C13 C -0.1296(2) 0.14781(18) 0.4249(2) 0.0156(6) Uani 1 1 d . . .
H19A H 0.2107 0.1431 0.0337 0.020 Uiso 1 1 d R . .
H19B H 0.2896 0.0907 0.1057 0.020 Uiso 1 1 d R . .
H19C H 0.3316 0.1670 0.0699 0.020 Uiso 1 1 d R . .
C14 C 0.0674(3) 0.01094(19) 0.3281(3) 0.0268(8) Uani 1 1 d . . .
H20A H 0.2960 0.0676 0.3028 0.035 Uiso 1 1 d R . .
H20B H 0.4136 0.0809 0.2766 0.035 Uiso 1 1 d R . .
C15 C -0.2538(3) 0.1470(2) 0.4191(2) 0.0200(7) Uani 1 1 d . . .
H21A H 0.4221 0.0455 0.4493 0.026 Uiso 1 1 d R . .
H21B H 0.3489 0.1131 0.4695 0.026 Uiso 1 1 d R . .
H21C H 0.4665 0.1264 0.4433 0.026 Uiso 1 1 d R . .
105

C16 C 0.4267(3) 0.2211(2) 0.2612(3) 0.0212(7) Uani 1 1 d . . .

C17 C 0.3991(3) 0.3010(2) 0.2361(3) 0.0271(8) Uani 1 1 d . . .
C18 C 0.2382(2) 0.17710(19) 0.1861(2) 0.0171(6) Uani 1 1 d . . .
C19 C 0.2704(3) 0.1414(2) 0.0894(3) 0.0285(8) Uani 1 1 d . . .
C20 C 0.3587(3) 0.09932(18) 0.3151(2) 0.0169(6) Uani 1 1 d . . .
C21 C 0.4027(3) 0.0953(2) 0.4304(3) 0.0270(8) Uani 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.01066(18) 0.00986(19) 0.00992(18) -0.00037(12) 0.00086(12) -0.00030(14)
F1 0.0338(12) 0.0361(13) 0.0205(10) 0.0039(8) 0.0061(9) -0.0179(10)
F2 0.0392(12) 0.0296(12) 0.0200(10) 0.0067(8) 0.0019(9) 0.0201(10)
F3 0.0314(10) 0.0209(10) 0.0111(8) -0.0027(7) 0.0028(7) 0.0017(8)
F4 0.0421(12) 0.0131(10) 0.0213(10) -0.0022(7) 0.0052(8) -0.0039(9)
F5 0.0276(11) 0.0268(12) 0.0275(11) -0.0103(8) -0.0101(9) 0.0025(9)
F6 0.0379(12) 0.0261(11) 0.0256(10) -0.0097(8) 0.0206(9) -0.0035(9)
F7 0.0175(9) 0.0349(13) 0.0315(11) -0.0003(9) 0.0129(8) -0.0030(9)
F8 0.0263(10) 0.0365(13) 0.0198(10) -0.0043(8) -0.0021(8) -0.0170(9)
F9 0.0263(11) 0.0192(11) 0.0368(12) 0.0095(9) -0.0003(9) -0.0062(9)
F10 0.0246(10) 0.0358(13) 0.0160(9) 0.0097(8) -0.0083(8) -0.0102(9)
F11 0.0450(14) 0.0205(11) 0.0334(12) 0.0110(9) -0.0113(10) -0.0055(10)
F12 0.0252(11) 0.0598(16) 0.0193(10) 0.0110(10) 0.0077(8) -0.0051(11)
F13 0.0405(13) 0.0353(13) 0.0326(12) -0.0177(10) 0.0088(10) 0.0064(11)
F14 0.0360(14) 0.0249(14) 0.156(3) -0.0414(17) 0.0472(18) -0.0184(12)
F15 0.0411(13) 0.0230(12) 0.0490(14) 0.0088(10) 0.0188(11) 0.0155(10)
F16 0.0159(10) 0.0623(17) 0.0352(13) 0.0125(11) -0.0003(9) 0.0045(10)
F17 0.0187(11) 0.098(2) 0.0378(13) -0.0396(14) 0.0161(10) -0.0095(12)
F18 0.0171(11) 0.0339(15) 0.091(2) 0.0069(13) 0.0098(12) -0.0071(10)
O1 0.0141(10) 0.0130(11) 0.0131(10) -0.0010(8) -0.0013(8) -0.0002(8)
O2 0.0151(10) 0.0102(10) 0.0146(10) -0.0009(8) 0.0047(8) 0.0010(8)
O3 0.0137(9) 0.0162(11) 0.0111(9) -0.0005(8) 0.0015(8) 0.0005(9)
O4 0.0142(10) 0.0147(11) 0.0149(10) 0.0010(8) -0.0012(8) -0.0032(9)
O5 0.0127(9) 0.0113(10) 0.0142(10) -0.0008(8) 0.0029(8) -0.0009(8)
O6 0.0156(10) 0.0173(12) 0.0196(11) -0.0033(8) 0.0035(9) 0.0005(9)
N1 0.0124(11) 0.0179(13) 0.0111(12) -0.0020(10) 0.0027(9) 0.0029(10)
C1 0.0097(12) 0.0147(15) 0.0143(14) 0.0016(11) 0.0008(10) 0.0005(11)
C2 0.0160(14) 0.0143(15) 0.0147(14) -0.0011(11) 0.0026(11) 0.0009(12)
C3 0.0104(12) 0.0104(14) 0.0159(14) -0.0007(11) 0.0033(10) -0.0007(11)
106

C4 0.0199(14) 0.0148(15) 0.0149(14) 0.0004(11) 0.0041(11) 0.0002(13)

C5 0.0190(14) 0.0137(15) 0.0153(14) -0.0023(11) 0.0052(11) 0.0019(12)
C6 0.0102(12) 0.0123(15) 0.0158(14) -0.0014(10) 0.0017(10) 0.0017(11)
C7 0.0112(12) 0.0165(16) 0.0112(13) 0.0008(10) -0.0006(10) -0.0004(11)
C8 0.0148(14) 0.0151(15) 0.0117(13) -0.0007(11) 0.0005(11) 0.0009(12)
C9 0.0157(14) 0.0163(15) 0.0154(14) 0.0013(11) 0.0000(11) -0.0007(12)
C10 0.0167(15) 0.0231(18) 0.0186(15) 0.0059(12) -0.0016(12) -0.0051(13)
C11 0.0174(14) 0.0120(15) 0.0174(14) -0.0009(11) 0.0040(12) -0.0037(12)
C12 0.0162(14) 0.0187(17) 0.0244(16) -0.0054(12) 0.0045(12) -0.0066(13)
C13 0.0147(13) 0.0208(16) 0.0115(13) 0.0019(11) 0.0025(11) -0.0022(12)
C14 0.0227(17) 0.0105(16) 0.050(2) -0.0079(14) 0.0148(15) -0.0071(14)
C15 0.0170(15) 0.0259(18) 0.0174(15) -0.0048(12) 0.0039(12) -0.0025(13)
C16 0.0175(14) 0.0215(17) 0.0251(17) 0.0010(13) 0.0045(12) -0.0026(14)
C17 0.0296(18) 0.0222(18) 0.0286(19) 0.0042(14) 0.0016(15) -0.0077(15)
C18 0.0134(14) 0.0227(17) 0.0154(14) 0.0032(12) 0.0022(11) 0.0026(13)
C19 0.0313(19) 0.038(2) 0.0147(16) -0.0026(14) -0.0007(13) 0.0056(17)
C20 0.0198(15) 0.0141(15) 0.0163(14) -0.0001(11) 0.0014(12) 0.0030(12)
C21 0.038(2) 0.0216(18) 0.0196(17) 0.0007(13) -0.0027(14) 0.0090(16)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O5 1.954(2) . ?
Cu1 O2 1.955(2) . ?
Cu1 O4 2.004(2) . ?
Cu1 O1 2.022(2) . ?
Cu1 O6 2.187(2) . ?
Cu1 O3 2.335(2) . ?
F1 C4 1.338(3) . ?
F2 C4 1.340(2) . ?
F3 C4 1.329(2) . ?
107

F4 C5 1.336(2) . ?
F5 C5 1.329(2) . ?
F6 C5 1.336(2) . ?
F7 C9 1.350(4) . ?
F8 C9 1.328(4) . ?
F9 C9 1.327(4) . ?
F10 C10 1.340(4) . ?
F11 C10 1.328(4) . ?
F12 C10 1.331(4) . ?
F13 C14 1.334(4) . ?
F14 C14 1.324(4) . ?
F15 C14 1.341(4) . ?
F16 C15 1.326(4) . ?
F17 C15 1.319(4) . ?
F18 C15 1.330(4) . ?
O1 C1 1.243(4) . ?
O2 C3 1.263(3) . ?
O3 C6 1.255(4) . ?
O4 C8 1.265(4) . ?
O5 C11 1.267(4) . ?
O6 C13 1.241(4) . ?
N1 C20 1.505(4) . ?
N1 C16 1.510(4) . ?
N1 C18 1.515(4) . ?
N1 H1 0.84(4) . ?
C1 C2 1.402(3) . ?
C1 C4 1.531(3) . ?
C2 C3 1.3829 . ?
C2 H2 0.9595 . ?
C3 C5 1.5321 . ?
C6 C7 1.395(4) . ?
C6 C9 1.538(4) . ?
C7 C8 1.396(4) . ?
C7 H7 0.9595 . ?
C8 C10 1.535(4) . ?
C11 C12 1.374(4) . ?
C11 C14 1.531(5) . ?
C12 C13 1.419(5) . ?
C12 H12 0.9593 . ?
C13 C15 1.535(4) . ?
C16 C17 1.509(5) . ?
C16 H16A 0.9599 . ?
C16 H16B 0.9650 . ?
C17 H17A 0.9705 . ?
108

C17 H17B 0.9629 . ?

C17 H17C 0.9558 . ?
C18 C19 1.510(5) . ?
C18 H18A 0.9642 . ?
C18 H18B 0.9587 . ?
C19 H19A 0.9555 . ?
C19 H19B 0.9622 . ?
C19 H19C 0.9543 . ?
C20 C21 1.509(4) . ?
C20 H20A 0.9623 . ?
C20 H20B 0.9604 . ?
C21 H21A 0.9544 . ?
C21 H21B 0.9513 . ?
C21 H21C 0.9669 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O5 Cu1 O2 177.33(9) . . ?
O5 Cu1 O4 88.42(8) . . ?
O2 Cu1 O4 89.22(9) . . ?
O5 Cu1 O1 90.28(8) . . ?
O2 Cu1 O1 91.76(8) . . ?
O4 Cu1 O1 167.56(8) . . ?
O5 Cu1 O6 89.47(8) . . ?
O2 Cu1 O6 92.15(8) . . ?
O4 Cu1 O6 99.54(8) . . ?
O1 Cu1 O6 92.82(8) . . ?
O5 Cu1 O3 93.48(8) . . ?
O2 Cu1 O3 85.04(8) . . ?
O4 Cu1 O3 84.29(8) . . ?
O1 Cu1 O3 83.43(8) . . ?
O6 Cu1 O3 175.23(8) . . ?
C1 O1 Cu1 122.26(19) . . ?
C3 O2 Cu1 123.19(15) . . ?
C6 O3 Cu1 115.84(18) . . ?
C8 O4 Cu1 126.6(2) . . ?
C11 O5 Cu1 125.86(19) . . ?
C13 O6 Cu1 122.3(2) . . ?
109

C20 N1 C16 111.6(2) . . ?

C20 N1 C18 111.9(2) . . ?
C16 N1 C18 113.5(2) . . ?
C20 N1 H1 105(3) . . ?
C16 N1 H1 108(3) . . ?
C18 N1 H1 107(3) . . ?
O1 C1 C2 128.7(3) . . ?
O1 C1 C4 115.9(2) . . ?
C2 C1 C4 115.4(2) . . ?
C3 C2 C1 121.90(14) . . ?
C3 C2 H2 120.0 . . ?
C1 C2 H2 118.1 . . ?
O2 C3 C2 128.68(11) . . ?
O2 C3 C5 113.00(11) . . ?
C2 C3 C5 118.3 . . ?
F3 C4 F1 107.43(16) . . ?
F3 C4 F2 107.34(16) . . ?
F1 C4 F2 106.45(18) . . ?
F3 C4 C1 112.26(18) . . ?
F1 C4 C1 111.53(17) . . ?
F2 C4 C1 111.53(17) . . ?
F5 C5 F4 107.95(17) . . ?
F5 C5 F6 107.39(17) . . ?
F4 C5 F6 107.11(17) . . ?
F5 C5 C3 110.20(11) . . ?
F4 C5 C3 112.93(10) . . ?
F6 C5 C3 111.04(11) . . ?
O3 C6 C7 128.1(3) . . ?
O3 C6 C9 114.5(3) . . ?
C7 C6 C9 117.4(2) . . ?
C6 C7 C8 122.9(3) . . ?
C6 C7 H7 117.7 . . ?
C8 C7 H7 119.4 . . ?
O4 C8 C7 129.4(3) . . ?
O4 C8 C10 112.3(3) . . ?
C7 C8 C10 118.3(3) . . ?
F8 C9 F9 108.0(3) . . ?
F8 C9 F7 106.9(2) . . ?
F9 C9 F7 106.6(2) . . ?
F8 C9 C6 114.1(3) . . ?
F9 C9 C6 110.7(2) . . ?
F7 C9 C6 110.1(3) . . ?
F11 C10 F12 107.6(3) . . ?
F11 C10 F10 107.4(3) . . ?
110

F12 C10 F10 107.2(3) . . ?

F11 C10 C8 109.8(3) . . ?
F12 C10 C8 111.5(3) . . ?
F10 C10 C8 113.1(3) . . ?
O5 C11 C12 130.8(3) . . ?
O5 C11 C14 112.1(3) . . ?
C12 C11 C14 117.1(3) . . ?
C11 C12 C13 122.6(3) . . ?
C11 C12 H12 116.9 . . ?
C13 C12 H12 120.5 . . ?
O6 C13 C12 127.9(3) . . ?
O6 C13 C15 115.4(3) . . ?
C12 C13 C15 116.7(3) . . ?
F14 C14 F13 108.2(3) . . ?
F14 C14 F15 106.7(3) . . ?
F13 C14 F15 106.2(3) . . ?
F14 C14 C11 113.3(3) . . ?
F13 C14 C11 111.5(3) . . ?
F15 C14 C11 110.6(3) . . ?
F17 C15 F16 106.9(3) . . ?
F17 C15 F18 107.7(3) . . ?
F16 C15 F18 106.0(3) . . ?
F17 C15 C13 111.9(3) . . ?
F16 C15 C13 110.2(3) . . ?
F18 C15 C13 113.8(3) . . ?
C17 C16 N1 112.2(3) . . ?
C17 C16 H16A 109.5 . . ?
N1 C16 H16A 109.3 . . ?
C17 C16 H16B 108.3 . . ?
N1 C16 H16B 108.3 . . ?
H16A C16 H16B 109.1 . . ?
C16 C17 H17A 110.0 . . ?
C16 C17 H17B 109.3 . . ?
H17A C17 H17B 108.4 . . ?
C16 C17 H17C 110.6 . . ?
H17A C17 H17C 108.9 . . ?
H17B C17 H17C 109.6 . . ?
C19 C18 N1 113.3(3) . . ?
C19 C18 H18A 107.5 . . ?
N1 C18 H18A 109.8 . . ?
C19 C18 H18B 107.0 . . ?
N1 C18 H18B 109.7 . . ?
H18A C18 H18B 109.4 . . ?
C18 C19 H19A 109.6 . . ?
111

C18 C19 H19B 108.2 . . ?

H19A C19 H19B 109.6 . . ?
C18 C19 H19C 109.1 . . ?
H19A C19 H19C 110.5 . . ?
H19B C19 H19C 109.8 . . ?
N1 C20 C21 112.8(3) . . ?
N1 C20 H20A 109.9 . . ?
C21 C20 H20A 107.7 . . ?
N1 C20 H20B 109.1 . . ?
C21 C20 H20B 108.1 . . ?
H20A C20 H20B 109.2 . . ?
C20 C21 H21A 109.8 . . ?
C20 C21 H21B 108.9 . . ?
H21A C21 H21B 110.8 . . ?
C20 C21 H21C 108.2 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.6 . . ?
_diffrn_measured_fraction_theta_max 0.944
_diffrn_reflns_theta_full
30.04
_diffrn_measured_fraction_theta_full 0.944
_refine_diff_density_max 1.030
_refine_diff_density_min -0.650
_refine_diff_density_rms 0.182
# END OF CIF

112

Table A-4. CIF File For (Et3NH)[Cu(hfac)3].H2O

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
triethylammonium tris(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)cuprate(II)
monohydrate
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety 'C6 H16 N1 1+, C15 H3 Cu O6 F18 1-, H2 O'
_chemical_formula_sum
'C21 H21 Cu F18 N O7'
_chemical_formula_weight
804.93
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
Triclinic
_symmetry_space_group_name_H-M P-1
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b
_cell_length_c

10.7570(5)
11.7170(5)
12.8520(5)
113

_cell_angle_alpha
91.949(3)
_cell_angle_beta
99.782(3)
_cell_angle_gamma
110.015(3)
_cell_volume
1492.45(11)
_cell_formula_units_Z
2
_cell_measurement_temperature 100
_cell_measurement_reflns_used 14109
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
27.5
_exptl_crystal_description
lath
_exptl_crystal_colour
yellow
_exptl_crystal_size_max
0.48
_exptl_crystal_size_mid
0.10
_exptl_crystal_size_min
0.05
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.791
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
802
_exptl_absorpt_coefficient_mu 0.886
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.6758
_exptl_absorpt_correction_T_max 0.9571
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
100
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
_diffrn_reflns_number
10812
_diffrn_reflns_av_R_equivalents 0.031
114

_diffrn_reflns_av_sigmaI/netI 0.0729
_diffrn_reflns_limit_h_min
-11
_diffrn_reflns_limit_h_max
13
_diffrn_reflns_limit_k_min
-15
_diffrn_reflns_limit_k_max
14
_diffrn_reflns_limit_l_min
-16
_diffrn_reflns_limit_l_max
16
_diffrn_reflns_theta_min
2.58
_diffrn_reflns_theta_max
27.53
_reflns_number_total
6763
_reflns_number_gt
4108
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0822P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
6763
115

_refine_ls_number_parameters
442
_refine_ls_number_restraints
2
_refine_ls_R_factor_all
0.0892
_refine_ls_R_factor_gt
0.0527
_refine_ls_wR_factor_ref
0.1517
_refine_ls_wR_factor_gt
0.1406
_refine_ls_goodness_of_fit_ref 1.015
_refine_ls_restrained_S_all
1.015
_refine_ls_shift/su_max
0.096
_refine_ls_shift/su_mean
0.002
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.36581(4) 0.27148(4) 0.24308(3) 0.03844(15) Uani 1 1 d . . .
F1 F -0.0752(2) 0.2351(2) -0.02909(16) 0.0592(6) Uani 1 1 d . . .
F2 F 0.0571(2) 0.41556(19) 0.03524(19) 0.0677(7) Uani 1 1 d . . .
F3 F -0.0475(2) 0.2927(2) 0.13670(16) 0.0572(6) Uani 1 1 d . . .
F4 F 0.1406(2) -0.03161(19) -0.11104(18) 0.0618(6) Uani 1 1 d . . .
F5 F 0.3375(3) -0.0192(2) -0.03543(18) 0.0778(8) Uani 1 1 d . . .
F6 F 0.3099(3) 0.1099(2) -0.14412(17) 0.0644(6) Uani 1 1 d . . .
F7 F 0.8507(3) 0.2562(3) 0.3564(4) 0.1412(17) Uani 1 1 d . . .
F8 F 0.6921(4) 0.0925(3) 0.2887(2) 0.1045(11) Uani 1 1 d . . .
F9 F 0.7009(3) 0.1672(3) 0.44034(18) 0.0837(8) Uani 1 1 d . . .
F10 F 0.8196(3) 0.5551(3) 0.1392(2) 0.0910(9) Uani 1 1 d . . .
F11 F 0.7200(3) 0.6519(2) 0.2118(2) 0.0850(8) Uani 1 1 d . . .
F12 F 0.6324(3) 0.5603(3) 0.05786(19) 0.0837(8) Uani 1 1 d . . .
F13 F 0.1421(3) 0.3512(2) 0.5717(2) 0.0843(8) Uani 1 1 d . . .
F14 F 0.1664(6) 0.4751(3) 0.4616(3) 0.154(2) Uani 1 1 d . . .
F15 F 0.3342(4) 0.4708(5) 0.5612(3) 0.178(2) Uani 1 1 d . . .
F16 F -0.0698(2) -0.0258(2) 0.36825(18) 0.0641(6) Uani 1 1 d . . .
F17 F 0.0997(3) -0.08313(19) 0.41386(16) 0.0652(6) Uani 1 1 d . . .
F18 F 0.0170(3) -0.0890(2) 0.24889(16) 0.0734(7) Uani 1 1 d . . .
116

O1 O 0.2149(2) 0.3126(2) 0.16784(17) 0.0399(5) Uani 1 1 d . . .

O2 O 0.3589(2) 0.1639(2) 0.09834(17) 0.0472(6) Uani 1 1 d . . .
O3 O 0.5161(2) 0.2266(2) 0.31427(17) 0.0426(5) Uani 1 1 d . . .
O4 O 0.5014(2) 0.4252(2) 0.20054(18) 0.0452(6) Uani 1 1 d . . .
O5 O 0.3353(3) 0.3596(2) 0.38286(19) 0.0517(6) Uani 1 1 d . . .
O6 O 0.2345(3) 0.1118(3) 0.2851(2) 0.0597(7) Uani 1 1 d . . .
O1W O 0.3454(3) 0.9382(3) 0.2268(3) 0.0654(8) Uani 1 1 d D . .
H1W H 0.334(5) 0.979(4) 0.281(3) 0.080 Uiso 1 1 d D . .
H2W H 0.399(4) 0.981(4) 0.183(3) 0.080 Uiso 1 1 d D . .
N1 N 0.3484(3) 0.7022(3) 0.2595(2) 0.0484(7) Uani 1 1 d . . .
H1 H 0.3454 0.7798 0.2514 0.058 Uiso 1 1 calc R . .
C1 C 0.1363(3) 0.2571(3) 0.0827(2) 0.0358(7) Uani 1 1 d . . .
C2 C 0.1479(3) 0.1702(3) 0.0126(2) 0.0380(7) Uani 1 1 d . . .
H2 H 0.0766 0.1345 -0.0466 0.046 Uiso 1 1 calc R . .
C3 C 0.2581(3) 0.1330(3) 0.0245(2) 0.0381(7) Uani 1 1 d . . .
C4 C 0.0165(4) 0.2995(3) 0.0561(3) 0.0466(9) Uani 1 1 d . . .
C5 C 0.2626(4) 0.0467(3) -0.0663(3) 0.0442(8) Uani 1 1 d . . .
C6 C 0.6334(4) 0.2670(3) 0.2970(2) 0.0408(8) Uani 1 1 d . . .
C7 C 0.6912(4) 0.3640(3) 0.2416(3) 0.0463(8) Uani 1 1 d . . .
H7 H 0.7809 0.3805 0.2313 0.056 Uiso 1 1 calc R . .
C8 C 0.6220(4) 0.4375(3) 0.2005(3) 0.0437(8) Uani 1 1 d . . .
C9 C 0.7212(4) 0.1959(4) 0.3457(3) 0.0575(10) Uani 1 1 d . . .
C10 C 0.6981(4) 0.5517(4) 0.1495(3) 0.0593(10) Uani 1 1 d . . .
C11 C 0.2336(4) 0.3150(3) 0.4227(3) 0.0459(9) Uani 1 1 d . . .
C12 C 0.1379(3) 0.1978(3) 0.4055(2) 0.0414(8) Uani 1 1 d . . .
H12 H 0.0624 0.1803 0.4394 0.050 Uiso 1 1 calc R . .
C13 C 0.1478(4) 0.1062(3) 0.3416(3) 0.0468(9) Uani 1 1 d . . .
C14 C 0.2176(5) 0.4008(4) 0.5065(3) 0.0631(11) Uani 1 1 d . . .
C15 C 0.0462(4) -0.0232(4) 0.3425(3) 0.0554(10) Uani 1 1 d . . .
C16 C 0.2045(4) 0.6133(3) 0.2433(3) 0.0538(9) Uani 1 1 d . . .
H16A H 0.1654 0.5976 0.1665 0.065 Uiso 1 1 calc R . .
H16B H 0.2049 0.5348 0.2693 0.065 Uiso 1 1 calc R . .
C17 C 0.1182(4) 0.6591(4) 0.2993(4) 0.0692(12) Uani 1 1 d . . .
H17A H 0.1583 0.6778 0.3751 0.104 Uiso 1 1 calc R . .
H17B H 0.0280 0.5966 0.2900 0.104 Uiso 1 1 calc R . .
H17C H 0.1114 0.7333 0.2698 0.104 Uiso 1 1 calc R . .
C18 C 0.4228(4) 0.7039(4) 0.3694(3) 0.0602(10) Uani 1 1 d . . .
H18A H 0.4498 0.6312 0.3731 0.072 Uiso 1 1 calc R . .
H18B H 0.3610 0.6979 0.4196 0.072 Uiso 1 1 calc R . .
C19 C 0.5481(4) 0.8180(4) 0.4046(4) 0.0774(14) Uani 1 1 d . . .
H19A H 0.6135 0.8210 0.3592 0.116 Uiso 1 1 calc R . .
H19B H 0.5885 0.8156 0.4785 0.116 Uiso 1 1 calc R . .
H19C H 0.5229 0.8907 0.3988 0.116 Uiso 1 1 calc R . .
C20 C 0.4194(4) 0.6735(4) 0.1778(3) 0.0642(11) Uani 1 1 d . . .
117

H20A H 0.4041 0.5851 0.1729 0.077 Uiso 1 1 calc R . .

H20B H 0.5176 0.7182 0.2004 0.077 Uiso 1 1 calc R . .
C21 C 0.3715(5) 0.7078(5) 0.0676(3) 0.0736(13) Uani 1 1 d . . .
H21A H 0.2770 0.6566 0.0410 0.110 Uiso 1 1 calc R . .
H21B H 0.4271 0.6948 0.0187 0.110 Uiso 1 1 calc R . .
H21C H 0.3798 0.7938 0.0730 0.110 Uiso 1 1 calc R . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0422(3) 0.0410(2) 0.0390(2) 0.00818(17) 0.01411(17) 0.01993(19)
F1 0.0514(13) 0.0728(14) 0.0573(13) -0.0052(11) -0.0033(10) 0.0346(12)
F2 0.0707(16) 0.0476(13) 0.0934(17) 0.0251(12) 0.0134(13) 0.0312(12)
F3 0.0510(13) 0.0673(14) 0.0621(13) -0.0018(11) 0.0191(10) 0.0289(11)
F4 0.0682(16) 0.0477(12) 0.0689(14) -0.0075(10) 0.0148(12) 0.0202(12)
F5 0.098(2) 0.0999(19) 0.0657(14) 0.0029(13) 0.0103(13) 0.0766(17)
F6 0.0857(18) 0.0616(13) 0.0510(12) 0.0039(10) 0.0350(12) 0.0222(13)
F7 0.0510(19) 0.136(3) 0.258(5) 0.103(3) 0.029(2) 0.053(2)
F8 0.176(3) 0.095(2) 0.0783(17) -0.0013(15) 0.0127(18) 0.100(2)
F9 0.098(2) 0.131(2) 0.0529(14) 0.0173(14) 0.0048(13) 0.0836(19)
F10 0.0465(15) 0.109(2) 0.127(2) 0.0596(18) 0.0369(15) 0.0251(15)
F11 0.089(2) 0.0611(16) 0.0949(19) 0.0183(15) 0.0178(15) 0.0131(14)
F12 0.0615(16) 0.104(2) 0.0660(14) 0.0451(14) 0.0002(12) 0.0070(14)
F13 0.112(2) 0.0741(16) 0.0731(16) 0.0041(13) 0.0588(16) 0.0220(16)
F14 0.317(6) 0.128(3) 0.109(2) 0.051(2) 0.104(3) 0.159(4)
F15 0.089(3) 0.238(5) 0.129(3) -0.115(3) 0.040(2) -0.036(3)
F16 0.0559(15) 0.0608(14) 0.0729(15) 0.0036(11) 0.0116(11) 0.0180(12)
F17 0.0856(18) 0.0538(13) 0.0536(12) 0.0067(10) -0.0091(11) 0.0317(12)
F18 0.0901(19) 0.0860(17) 0.0451(12) -0.0148(11) -0.0123(12) 0.0465(15)
O1 0.0444(14) 0.0430(12) 0.0377(12) 0.0031(10) 0.0084(10) 0.0220(11)
O2 0.0398(14) 0.0628(15) 0.0403(12) 0.0088(11) 0.0057(11) 0.0204(12)
O3 0.0428(15) 0.0460(13) 0.0446(12) 0.0078(10) 0.0119(10) 0.0206(12)
O4 0.0344(14) 0.0574(14) 0.0480(13) 0.0140(11) 0.0090(10) 0.0200(12)
O5 0.0431(15) 0.0670(16) 0.0537(14) 0.0231(12) 0.0187(12) 0.0242(13)
O6 0.082(2) 0.0715(17) 0.0582(15) 0.0268(13) 0.0361(14) 0.0555(16)
O1W 0.070(2) 0.0518(17) 0.085(2) 0.0090(15) 0.0229(16) 0.0311(15)
N1 0.0447(18) 0.0559(18) 0.0532(17) 0.0092(14) 0.0107(14) 0.0279(15)
C1 0.0373(19) 0.0356(17) 0.0378(17) 0.0129(14) 0.0113(14) 0.0144(15)
C2 0.0368(19) 0.0425(18) 0.0370(16) 0.0070(14) 0.0075(14) 0.0164(15)
118

C3 0.0383(19) 0.0404(18) 0.0374(17) 0.0112(14) 0.0137(15) 0.0125(15)

C4 0.044(2) 0.047(2) 0.051(2) 0.0062(16) 0.0074(17) 0.0183(17)
C5 0.047(2) 0.052(2) 0.0424(18) 0.0105(16) 0.0119(16) 0.0262(19)
C6 0.039(2) 0.0468(19) 0.0378(17) -0.0031(15) 0.0056(14) 0.0180(17)
C7 0.0354(19) 0.062(2) 0.0443(18) 0.0033(17) 0.0054(15) 0.0214(18)
C8 0.035(2) 0.053(2) 0.0382(17) 0.0050(15) 0.0087(14) 0.0084(17)
C9 0.056(3) 0.064(3) 0.062(3) 0.005(2) 0.0095(19) 0.034(2)
C10 0.043(2) 0.071(3) 0.064(2) 0.020(2) 0.0120(19) 0.018(2)
C11 0.042(2) 0.061(2) 0.0378(18) 0.0119(16) 0.0087(15) 0.0207(19)
C12 0.040(2) 0.057(2) 0.0340(16) 0.0082(15) 0.0097(14) 0.0232(17)
C13 0.050(2) 0.066(2) 0.0390(18) 0.0186(17) 0.0103(16) 0.0374(19)
C14 0.072(3) 0.057(2) 0.057(2) 0.007(2) 0.027(2) 0.012(2)
C15 0.072(3) 0.064(2) 0.0389(19) 0.0049(18) 0.0001(18) 0.040(2)
C16 0.047(2) 0.045(2) 0.066(2) 0.0092(18) 0.0099(18) 0.0125(18)
C17 0.050(3) 0.074(3) 0.084(3) 0.002(2) 0.013(2) 0.024(2)
C18 0.051(2) 0.066(2) 0.065(2) 0.020(2) 0.0058(19) 0.023(2)
C19 0.053(3) 0.083(3) 0.080(3) 0.030(3) -0.005(2) 0.011(2)
C20 0.060(3) 0.065(3) 0.083(3) 0.013(2) 0.026(2) 0.036(2)
C21 0.070(3) 0.097(3) 0.063(3) 0.006(2) 0.025(2) 0.036(3)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O1 1.959(2) . ?
Cu1 O3 1.959(2) . ?
Cu1 O4 2.052(2) . ?
Cu1 O6 2.075(3) . ?
Cu1 O5 2.170(3) . ?
Cu1 O2 2.187(2) . ?
F1 C4 1.345(4) . ?
F2 C4 1.330(4) . ?
119

F3 C4 1.328(4) . ?
F4 C5 1.334(4) . ?
F5 C5 1.320(4) . ?
F6 C5 1.332(4) . ?
F7 C9 1.309(5) . ?
F8 C9 1.306(5) . ?
F9 C9 1.307(5) . ?
F10 C10 1.324(5) . ?
F11 C10 1.326(5) . ?
F12 C10 1.292(4) . ?
F13 C14 1.280(5) . ?
F14 C14 1.284(6) . ?
F15 C14 1.303(5) . ?
F16 C15 1.335(5) . ?
F17 C15 1.344(4) . ?
F18 C15 1.336(4) . ?
O1 C1 1.263(4) . ?
O2 C3 1.251(4) . ?
O3 C6 1.248(4) . ?
O4 C8 1.255(4) . ?
O5 C11 1.244(4) . ?
O6 C13 1.262(4) . ?
O1W H1W 0.885(19) . ?
O1W H2W 0.914(19) . ?
N1 C20 1.491(5) . ?
N1 C18 1.497(5) . ?
N1 C16 1.516(5) . ?
N1 H1 0.9300 . ?
C1 C2 1.388(4) . ?
C1 C4 1.525(5) . ?
C2 C3 1.384(5) . ?
C2 H2 0.9500 . ?
C3 C5 1.535(5) . ?
C6 C7 1.381(5) . ?
C6 C9 1.534(5) . ?
C7 C8 1.383(5) . ?
C7 H7 0.9500 . ?
C8 C10 1.543(5) . ?
C11 C12 1.389(5) . ?
C11 C14 1.520(5) . ?
C12 C13 1.373(5) . ?
C12 H12 0.9500 . ?
C13 C15 1.538(6) . ?
C16 C17 1.487(6) . ?
120

C16 H16A 0.9900 . ?

C16 H16B 0.9900 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?
C18 C19 1.526(6) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C20 C21 1.538(6) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Cu1 O3 178.10(9) . . ?
O1 Cu1 O4 90.79(9) . . ?
O3 Cu1 O4 89.51(9) . . ?
O1 Cu1 O6 91.26(10) . . ?
O3 Cu1 O6 88.39(10) . . ?
O4 Cu1 O6 177.40(9) . . ?
O1 Cu1 O5 85.04(9) . . ?
O3 Cu1 O5 96.79(9) . . ?
O4 Cu1 O5 96.21(10) . . ?
O6 Cu1 O5 85.56(10) . . ?
O1 Cu1 O2 88.82(9) . . ?
O3 Cu1 O2 89.29(9) . . ?
O4 Cu1 O2 91.79(10) . . ?
O6 Cu1 O2 86.65(10) . . ?
O5 Cu1 O2 169.97(9) . . ?
C1 O1 Cu1 125.93(19) . . ?
C3 O2 Cu1 121.0(2) . . ?
C6 O3 Cu1 124.9(2) . . ?
121

C8 O4 Cu1 123.1(2) . . ?
C11 O5 Cu1 122.3(2) . . ?
C13 O6 Cu1 125.2(2) . . ?
H1W O1W H2W 118(4) . . ?
C20 N1 C18 111.5(3) . . ?
C20 N1 C16 111.0(3) . . ?
C18 N1 C16 110.8(3) . . ?
C20 N1 H1 107.8 . . ?
C18 N1 H1 107.8 . . ?
C16 N1 H1 107.8 . . ?
O1 C1 C2 129.3(3) . . ?
O1 C1 C4 111.9(3) . . ?
C2 C1 C4 118.7(3) . . ?
C3 C2 C1 123.4(3) . . ?
C3 C2 H2 118.3 . . ?
C1 C2 H2 118.3 . . ?
O2 C3 C2 128.6(3) . . ?
O2 C3 C5 114.6(3) . . ?
C2 C3 C5 116.8(3) . . ?
F3 C4 F2 106.8(3) . . ?
F3 C4 F1 107.2(3) . . ?
F2 C4 F1 106.6(3) . . ?
F3 C4 C1 111.6(3) . . ?
F2 C4 C1 110.7(3) . . ?
F1 C4 C1 113.5(3) . . ?
F5 C5 F6 108.7(3) . . ?
F5 C5 F4 106.7(3) . . ?
F6 C5 F4 105.3(3) . . ?
F5 C5 C3 112.9(3) . . ?
F6 C5 C3 110.3(3) . . ?
F4 C5 C3 112.6(3) . . ?
O3 C6 C7 129.0(3) . . ?
O3 C6 C9 113.1(3) . . ?
C7 C6 C9 117.9(3) . . ?
C6 C7 C8 121.7(3) . . ?
C6 C7 H7 119.1 . . ?
C8 C7 H7 119.1 . . ?
O4 C8 C7 128.0(3) . . ?
O4 C8 C10 113.4(3) . . ?
C7 C8 C10 118.6(3) . . ?
F8 C9 F9 105.7(4) . . ?
F8 C9 F7 108.3(4) . . ?
F9 C9 F7 106.0(4) . . ?
F8 C9 C6 110.9(3) . . ?
122

F9 C9 C6 112.0(3) . . ?
F7 C9 C6 113.5(3) . . ?
F12 C10 F10 108.8(4) . . ?
F12 C10 F11 108.0(4) . . ?
F10 C10 F11 104.8(3) . . ?
F12 C10 C8 112.6(3) . . ?
F10 C10 C8 112.2(3) . . ?
F11 C10 C8 110.2(3) . . ?
O5 C11 C12 129.6(3) . . ?
O5 C11 C14 114.2(3) . . ?
C12 C11 C14 116.1(3) . . ?
C13 C12 C11 122.7(3) . . ?
C13 C12 H12 118.6 . . ?
C11 C12 H12 118.6 . . ?
O6 C13 C12 128.7(4) . . ?
O6 C13 C15 114.1(3) . . ?
C12 C13 C15 117.1(3) . . ?
F13 C14 F14 105.7(4) . . ?
F13 C14 F15 108.2(4) . . ?
F14 C14 F15 104.4(5) . . ?
F13 C14 C11 116.5(3) . . ?
F14 C14 C11 109.8(3) . . ?
F15 C14 C11 111.3(4) . . ?
F16 C15 F18 107.8(3) . . ?
F16 C15 F17 106.8(3) . . ?
F18 C15 F17 106.3(3) . . ?
F16 C15 C13 114.0(3) . . ?
F18 C15 C13 111.8(3) . . ?
F17 C15 C13 109.8(3) . . ?
C17 C16 N1 112.6(3) . . ?
C17 C16 H16A 109.1 . . ?
N1 C16 H16A 109.1 . . ?
C17 C16 H16B 109.1 . . ?
N1 C16 H16B 109.1 . . ?
H16A C16 H16B 107.8 . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C16 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
N1 C18 C19 113.7(3) . . ?
N1 C18 H18A 108.8 . . ?
C19 C18 H18A 108.8 . . ?
123

N1 C18 H18B 108.8 . . ?

C19 C18 H18B 108.8 . . ?
H18A C18 H18B 107.7 . . ?
C18 C19 H19A 109.5 . . ?
C18 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C18 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
N1 C20 C21 112.7(3) . . ?
N1 C20 H20A 109.1 . . ?
C21 C20 H20A 109.1 . . ?
N1 C20 H20B 109.1 . . ?
C21 C20 H20B 109.1 . . ?
H20A C20 H20B 107.8 . . ?
C20 C21 H21A 109.5 . . ?
C20 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C20 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O3 Cu1 O1 C1 10(3) . . . . ?
O4 Cu1 O1 C1 109.2(3) . . . . ?
O6 Cu1 O1 C1 -69.2(3) . . . . ?
O5 Cu1 O1 C1 -154.6(3) . . . . ?
O2 Cu1 O1 C1 17.4(3) . . . . ?
O1 Cu1 O2 C3 -16.1(2) . . . . ?
O3 Cu1 O2 C3 163.6(3) . . . . ?
O4 Cu1 O2 C3 -106.9(2) . . . . ?
O6 Cu1 O2 C3 75.2(2) . . . . ?
O5 Cu1 O2 C3 36.1(6) . . . . ?
O1 Cu1 O3 C6 80(3) . . . . ?
124

O4 Cu1 O3 C6 -19.3(3) . . . . ?
O6 Cu1 O3 C6 159.1(3) . . . . ?
O5 Cu1 O3 C6 -115.5(3) . . . . ?
O2 Cu1 O3 C6 72.5(3) . . . . ?
O1 Cu1 O4 C8 -159.8(3) . . . . ?
O3 Cu1 O4 C8 18.3(3) . . . . ?
O6 Cu1 O4 C8 -18(2) . . . . ?
O5 Cu1 O4 C8 115.1(3) . . . . ?
O2 Cu1 O4 C8 -70.9(3) . . . . ?
O1 Cu1 O5 C11 68.8(3) . . . . ?
O3 Cu1 O5 C11 -110.7(3) . . . . ?
O4 Cu1 O5 C11 159.1(3) . . . . ?
O6 Cu1 O5 C11 -22.8(3) . . . . ?
O2 Cu1 O5 C11 16.4(6) . . . . ?
O1 Cu1 O6 C13 -61.5(3) . . . . ?
O3 Cu1 O6 C13 120.3(3) . . . . ?
O4 Cu1 O6 C13 156(2) . . . . ?
O5 Cu1 O6 C13 23.4(3) . . . . ?
O2 Cu1 O6 C13 -150.3(3) . . . . ?
Cu1 O1 C1 C2 -11.9(5) . . . . ?
Cu1 O1 C1 C4 170.4(2) . . . . ?
O1 C1 C2 C3 -3.1(5) . . . . ?
C4 C1 C2 C3 174.4(3) . . . . ?
Cu1 O2 C3 C2 9.1(5) . . . . ?
Cu1 O2 C3 C5 -173.9(2) . . . . ?
C1 C2 C3 O2 3.5(6) . . . . ?
C1 C2 C3 C5 -173.4(3) . . . . ?
O1 C1 C4 F3 -53.3(4) . . . . ?
C2 C1 C4 F3 128.8(3) . . . . ?
O1 C1 C4 F2 65.6(4) . . . . ?
C2 C1 C4 F2 -112.3(3) . . . . ?
O1 C1 C4 F1 -174.6(3) . . . . ?
C2 C1 C4 F1 7.5(4) . . . . ?
O2 C3 C5 F5 26.3(4) . . . . ?
C2 C3 C5 F5 -156.3(3) . . . . ?
O2 C3 C5 F6 -95.5(3) . . . . ?
C2 C3 C5 F6 81.9(4) . . . . ?
O2 C3 C5 F4 147.2(3) . . . . ?
C2 C3 C5 F4 -35.4(4) . . . . ?
Cu1 O3 C6 C7 12.4(5) . . . . ?
Cu1 O3 C6 C9 -167.5(2) . . . . ?
O3 C6 C7 C8 4.0(6) . . . . ?
C9 C6 C7 C8 -176.1(3) . . . . ?
Cu1 O4 C8 C7 -10.2(5) . . . . ?
125

Cu1 O4 C8 C10 171.2(2) . . . . ?

C6 C7 C8 O4 -4.7(6) . . . . ?
C6 C7 C8 C10 173.9(3) . . . . ?
O3 C6 C9 F8 77.1(4) . . . . ?
C7 C6 C9 F8 -102.8(4) . . . . ?
O3 C6 C9 F9 -40.8(4) . . . . ?
C7 C6 C9 F9 139.3(4) . . . . ?
O3 C6 C9 F7 -160.8(4) . . . . ?
C7 C6 C9 F7 19.3(5) . . . . ?
O4 C8 C10 F12 -49.5(5) . . . . ?
C7 C8 C10 F12 131.7(4) . . . . ?
O4 C8 C10 F10 -172.6(3) . . . . ?
C7 C8 C10 F10 8.6(5) . . . . ?
O4 C8 C10 F11 71.0(4) . . . . ?
C7 C8 C10 F11 -107.8(4) . . . . ?
Cu1 O5 C11 C12 14.6(5) . . . . ?
Cu1 O5 C11 C14 -169.0(2) . . . . ?
O5 C11 C12 C13 4.2(6) . . . . ?
C14 C11 C12 C13 -172.2(3) . . . . ?
Cu1 O6 C13 C12 -15.3(5) . . . . ?
Cu1 O6 C13 C15 168.8(2) . . . . ?
C11 C12 C13 O6 -4.5(5) . . . . ?
C11 C12 C13 C15 171.3(3) . . . . ?
O5 C11 C14 F13 -159.5(4) . . . . ?
C12 C11 C14 F13 17.5(5) . . . . ?
O5 C11 C14 F14 80.4(5) . . . . ?
C12 C11 C14 F14 -102.6(4) . . . . ?
O5 C11 C14 F15 -34.7(5) . . . . ?
C12 C11 C14 F15 142.2(4) . . . . ?
O6 C13 C15 F16 -157.3(3) . . . . ?
C12 C13 C15 F16 26.3(4) . . . . ?
O6 C13 C15 F18 -34.7(4) . . . . ?
C12 C13 C15 F18 148.8(3) . . . . ?
O6 C13 C15 F17 83.0(4) . . . . ?
C12 C13 C15 F17 -93.4(4) . . . . ?
C20 N1 C16 C17 -162.2(3) . . . . ?
C18 N1 C16 C17 73.4(4) . . . . ?
C20 N1 C18 C19 75.6(4) . . . . ?
C16 N1 C18 C19 -160.3(4) . . . . ?
C18 N1 C20 C21 -162.9(3) . . . . ?
C16 N1 C20 C21 73.1(4) . . . . ?
loop_
_geom_hbond_atom_site_label_D
126

_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1 O1W 0.93 1.89 2.821(4) 176.0 .
O1W H1W O6 0.885(19) 2.17(4) 2.826(4) 131(4) 1_565
O1W H2W O2 0.914(19) 2.56(4) 3.140(4) 122(4) 1_565
_diffrn_measured_fraction_theta_max 0.986
_diffrn_reflns_theta_full
27.53
_diffrn_measured_fraction_theta_full 0.986
_refine_diff_density_max 0.602
_refine_diff_density_min -0.457
_refine_diff_density_rms 0.072
#END OF CIF

127

Table A-5. CIF File For (Et3NH)[Cu2(hfac)4(:-OH)]

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
triethylammonium
mu-hydroxotetrakis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)dicuprate(II)
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety
'C6 H16 N1 1+, C20 H5 Cu2 O9 F18 1-'
_chemical_formula_sum
'C26 H21 Cu2 F24 N O9'
_chemical_formula_weight
1074.52
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
triclinic
_symmetry_space_group_name_H-M P-1
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a
_cell_length_b

9.396(2)
11.998(3)
128

_cell_length_c
18.353(5)
_cell_angle_alpha
93.892(13)
_cell_angle_beta
102.170(14)
_cell_angle_gamma
108.929(14)
_cell_volume
1892.2(8)
_cell_formula_units_Z
2
_cell_measurement_temperature 170
_cell_measurement_reflns_used 21176
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
30.0
_exptl_crystal_description
fragment
_exptl_crystal_colour
'emerald green'
_exptl_crystal_size_max
0.40
_exptl_crystal_size_mid
0.35
_exptl_crystal_size_min
0.22
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.886
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
1060
_exptl_absorpt_coefficient_mu 1.292
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.596
_exptl_absorpt_correction_T_max 0.753
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
170
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
_diffrn_reflns_number 18538
129

_diffrn_reflns_av_R_equivalents 0.031
_diffrn_reflns_av_sigmaI/netI 0.0431
_diffrn_reflns_limit_h_min
0
_diffrn_reflns_limit_h_max
13
_diffrn_reflns_limit_k_min
-16
_diffrn_reflns_limit_k_max
15
_diffrn_reflns_limit_l_min
-25
_diffrn_reflns_limit_l_max
24
_diffrn_reflns_theta_min
2.7
_diffrn_reflns_theta_max
30.0
_reflns_number_total
10952
_reflns_number_gt
7417
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1172P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
130

_refine_ls_number_reflns
10952
_refine_ls_number_parameters
667
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.078
_refine_ls_R_factor_gt
0.054
_refine_ls_wR_factor_ref
0.181
_refine_ls_wR_factor_gt
0.167
_refine_ls_goodness_of_fit_ref 1.075
_refine_ls_restrained_S_all
1.075
_refine_ls_shift/su_max
0.002
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.54474(4) 0.36712(3) 0.695199(18) 0.03366(11) Uani 1 1 d . . .
Cu2 Cu 0.51250(4) 0.21180(3) 0.819500(19) 0.03722(12) Uani 1 1 d . . .
O1 O 0.4188(2) 0.31891(18) 0.76887(11) 0.0378(4) Uani 1 1 d . . .
H1OH H 0.4541 0.3780 0.8025 0.057 Uiso 1 1 d R . .
O2 O 0.6833(2) 0.3819(2) 0.62790(12) 0.0454(5) Uani 1 1 d . . .
O3 O 0.3614(2) 0.3005(2) 0.61194(12) 0.0458(5) Uani 1 1 d . . .
O4 O 0.7279(2) 0.42863(18) 0.78194(11) 0.0398(4) Uani 1 1 d . . .
O5 O 0.5479(3) 0.55096(19) 0.69069(13) 0.0474(5) Uani 1 1 d . . .
O6 O 0.6448(3) 0.1266(2) 0.86734(13) 0.0491(5) Uani 1 1 d . . .
O7 O 0.5228(2) 0.29534(19) 0.91546(11) 0.0426(5) Uani 1 1 d . . .
O8 O 0.5297(3) 0.15163(19) 0.72123(12) 0.0444(5) Uani 1 1 d . . .
O9 O 0.3037(3) 0.0532(2) 0.80903(13) 0.0521(6) Uani 1 1 d . . .
N1 N 0.0877(3) 0.2704(3) 0.74612(16) 0.0513(7) Uani 1 1 d . . .
H1N H 0.1961 0.2816 0.7497 0.077 Uiso 1 1 d R . .
C1 C 0.7715(5) 0.3982(5) 0.5180(2) 0.0762(13) Uani 1 1 d . . .
C2 C 0.6401(4) 0.3758(3) 0.55834(18) 0.0466(7) Uani 1 1 d . . .
C3 C 0.4925(4) 0.3474(3) 0.51375(18) 0.0501(8) Uani 1 1 d . . .
131

H3 H 0.4779 0.3555 0.4618 0.060 Uiso 1 1 calc R . .

C4 C 0.3655(4) 0.3074(3) 0.54370(18) 0.0515(8) Uani 1 1 d . . .
C5 C 0.2042(5) 0.2561(7) 0.4886(3) 0.099(2) Uani 1 1 d . . .
C6 C 0.8959(3) 0.5412(3) 0.89490(17) 0.0459(7) Uani 1 1 d . . .
C7 C 0.7715(3) 0.5292(3) 0.82164(15) 0.0384(6) Uani 1 1 d . . .
C8 C 0.7306(4) 0.6271(3) 0.80896(17) 0.0450(7) Uani 1 1 d . . .
H8 H 0.7765 0.6958 0.8463 0.054 Uiso 1 1 calc R . .
C9 C 0.6246(4) 0.6312(3) 0.74388(17) 0.0417(6) Uani 1 1 d . . .
C10 C 0.5978(5) 0.7496(3) 0.7350(2) 0.0581(9) Uani 1 1 d . . .
C11 C 0.7707(5) 0.0421(4) 0.9609(3) 0.0665(10) Uani 1 1 d . . .
C12 C 0.6836(4) 0.1268(3) 0.93686(19) 0.0462(7) Uani 1 1 d . . .
C13 C 0.6561(4) 0.1932(3) 0.99463(18) 0.0475(7) Uani 1 1 d . . .
H13 H 0.6903 0.1833 1.0455 0.057 Uiso 1 1 calc R . .
C14 C 0.5799(3) 0.2730(3) 0.97864(17) 0.0432(7) Uani 1 1 d . . .
C15 C 0.5593(5) 0.3479(4) 1.0446(2) 0.0591(9) Uani 1 1 d . . .
C16 C 0.5018(5) 0.0292(3) 0.6114(2) 0.0608(10) Uani 1 1 d . . .
C17 C 0.4523(4) 0.0501(3) 0.68328(17) 0.0441(7) Uani 1 1 d . . .
C18 C 0.3325(4) -0.0401(3) 0.69785(19) 0.0494(7) Uani 1 1 d . . .
H18 H 0.2902 -0.1128 0.6640 0.059 Uiso 1 1 calc R . .
C19 C 0.2680(4) -0.0315(3) 0.76008(18) 0.0450(7) Uani 1 1 d . . .
C20 C 0.1334(5) -0.1428(3) 0.7683(2) 0.0618(10) Uani 1 1 d . . .
C21A C 0.0209(8) 0.1960(9) 0.7985(5) 0.068(2) Uani 0.50 1 d P . .
C21B C 0.0718(13) 0.3009(8) 0.8287(5) 0.075(2) Uani 0.50 1 d P . .
C22 C 0.1286(6) 0.2413(5) 0.8826(3) 0.0833(13) Uani 1 1 d . . .
C23A C -0.0012(8) 0.2247(7) 0.6617(4) 0.0573(17) Uani 0.50 1 d P . .
C23B C -0.0068(10) 0.1349(7) 0.7233(6) 0.075(3) Uani 0.50 1 d P . .
C24 C 0.0130(6) 0.0967(4) 0.6446(3) 0.0862(15) Uani 1 1 d . . .
C25A C 0.0846(9) 0.4017(7) 0.7591(5) 0.0601(19) Uani 0.50 1 d P . .
C25B C 0.0393(9) 0.3475(7) 0.6976(5) 0.062(2) Uani 0.50 1 d P . .
C26 C 0.1612(5) 0.4793(4) 0.7157(3) 0.0698(11) Uani 1 1 d . . .
F1 F 0.9032(3) 0.4747(4) 0.55919(16) 0.1164(13) Uani 1 1 d . . .
F2 F 0.7400(3) 0.4395(4) 0.45361(16) 0.1211(14) Uani 1 1 d . . .
F3 F 0.8017(4) 0.2987(4) 0.5057(2) 0.1314(14) Uani 1 1 d . . .
F4 F 0.0992(3) 0.2858(4) 0.51354(15) 0.1031(11) Uani 1 1 d . . .
F5 F 0.1615(4) 0.1445(5) 0.4737(4) 0.226(4) Uani 1 1 d . . .
F6 F 0.2090(4) 0.3065(6) 0.42254(16) 0.157(2) Uani 1 1 d . . .
F7 F 0.9068(4) 0.6243(4) 0.94756(14) 0.1166(13) Uani 1 1 d . . .
F8 F 1.0345(2) 0.5683(2) 0.88199(13) 0.0642(6) Uani 1 1 d . . .
F9 F 0.8714(3) 0.4408(3) 0.92292(16) 0.1049(12) Uani 1 1 d . . .
F10A F 0.6840(14) 0.8339(6) 0.7918(5) 0.091(2) Uani 0.50 1 d P . .
F10B F 0.558(2) 0.7932(11) 0.7911(7) 0.131(4) Uani 0.50 1 d P . .
F11A F 0.4579(10) 0.7368(8) 0.7332(9) 0.096(3) Uani 0.50 1 d P . .
F11B F 0.4732(18) 0.7379(8) 0.6788(9) 0.149(5) Uani 0.50 1 d P . .
F12A F 0.6375(19) 0.7868(7) 0.6763(4) 0.106(5) Uani 0.50 1 d P . .
132

F12B F 0.7091(14) 0.8328(10) 0.7210(13) 0.159(6) Uani 0.50 1 d P . .

F13 F 0.8334(4) 0.0115(3) 0.90903(19) 0.1022(10) Uani 1 1 d . . .
F14 F 0.6868(6) -0.0498(4) 0.9767(5) 0.245(4) Uani 1 1 d . . .
F15 F 0.8957(5) 0.0926(4) 1.0156(2) 0.1460(17) Uani 1 1 d . . .
F16 F 0.4142(3) 0.3361(3) 1.03695(14) 0.0779(7) Uani 1 1 d . . .
F17 F 0.6392(3) 0.4630(2) 1.04621(15) 0.0811(7) Uani 1 1 d . . .
F18 F 0.6134(4) 0.3216(3) 1.11123(12) 0.0855(8) Uani 1 1 d . . .
F19A F 0.6439(7) 0.0205(8) 0.6332(4) 0.0810(17) Uani 0.50 1 d P . .
F19B F 0.6309(16) 0.1118(16) 0.6058(7) 0.183(7) Uani 0.50 1 d P . .
F20A F 0.4196(10) -0.0771(7) 0.5732(5) 0.087(3) Uani 0.50 1 d P . .
F20B F 0.514(3) -0.0642(11) 0.5932(8) 0.173(8) Uani 0.50 1 d P . .
F21A F 0.511(2) 0.1090(7) 0.5744(5) 0.113(5) Uani 0.50 1 d P . .
F21B F 0.404(2) 0.0466(17) 0.5514(5) 0.167(6) Uani 0.50 1 d P . .
F22A F 0.0531(16) -0.1122(11) 0.8136(6) 0.118(6) Uani 0.50 1 d P . .
F22B F 0.0160(12) -0.1214(9) 0.7686(12) 0.131(5) Uani 0.50 1 d P . .
F23A F 0.1949(15) -0.2133(11) 0.8047(9) 0.112(5) Uani 0.50 1 d P . .
F23B F 0.1697(15) -0.1934(11) 0.8222(6) 0.125(7) Uani 0.50 1 d P . .
F24A F 0.0455(18) -0.2009(15) 0.7069(6) 0.152(9) Uani 0.50 1 d P . .
F24B F 0.089(2) -0.2288(13) 0.7120(9) 0.146(7) Uani 0.50 1 d P . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.03161(18) 0.03683(19) 0.02997(19) 0.00271(13) 0.00299(13) 0.01184(14)
Cu2 0.0396(2) 0.0403(2) 0.03009(19) 0.00206(14) 0.00803(14) 0.01263(15)
O1 0.0381(10) 0.0409(11) 0.0331(10) -0.0008(8) 0.0068(8) 0.0145(8)
O2 0.0373(10) 0.0632(14) 0.0354(11) 0.0136(10) 0.0062(9) 0.0175(10)
O3 0.0358(10) 0.0572(13) 0.0354(11) -0.0096(9) 0.0021(8) 0.0118(9)
O4 0.0353(10) 0.0463(11) 0.0346(10) 0.0053(9) 0.0006(8) 0.0149(9)
O5 0.0533(12) 0.0400(11) 0.0421(12) 0.0019(9) -0.0045(10) 0.0181(10)
O6 0.0571(13) 0.0485(12) 0.0437(13) 0.0062(10) 0.0075(10) 0.0242(10)
O7 0.0450(11) 0.0493(12) 0.0317(11) -0.0008(9) 0.0068(9) 0.0171(9)
O8 0.0598(13) 0.0410(11) 0.0367(11) 0.0044(9) 0.0196(10) 0.0186(10)
O9 0.0550(13) 0.0465(12) 0.0447(13) 0.0008(10) 0.0170(10) 0.0023(10)
N1 0.0437(14) 0.0551(16) 0.0493(16) -0.0083(12) 0.0057(12) 0.0161(12)
C1 0.055(2) 0.132(4) 0.045(2) 0.029(2) 0.0190(18) 0.030(3)
C2 0.0479(17) 0.0607(19) 0.0375(16) 0.0166(14) 0.0129(13) 0.0238(15)
C3 0.0533(18) 0.072(2) 0.0295(15) 0.0062(14) 0.0042(13) 0.0316(16)
C4 0.0419(16) 0.073(2) 0.0343(16) -0.0129(15) -0.0048(13) 0.0258(15)
133

C5 0.053(2) 0.174(6) 0.051(3) -0.036(3) -0.009(2) 0.039(3)

C6 0.0342(14) 0.063(2) 0.0345(15) 0.0043(14) 0.0029(12) 0.0137(13)
C7 0.0291(12) 0.0553(17) 0.0259(13) 0.0041(12) 0.0056(10) 0.0091(12)
C8 0.0483(16) 0.0453(16) 0.0345(15) -0.0033(12) 0.0049(13) 0.0122(13)
C9 0.0475(16) 0.0360(14) 0.0401(16) 0.0053(12) 0.0107(13) 0.0127(12)
C10 0.076(3) 0.0464(19) 0.054(2) 0.0023(16) 0.0115(18) 0.0281(18)
C11 0.077(3) 0.068(2) 0.065(3) 0.026(2) 0.016(2) 0.037(2)
C12 0.0456(16) 0.0412(16) 0.0478(18) 0.0109(13) 0.0074(14) 0.0112(13)
C13 0.0514(18) 0.0491(17) 0.0372(16) 0.0112(13) 0.0071(13) 0.0126(14)
C14 0.0360(14) 0.0487(17) 0.0339(15) -0.0018(12) 0.0060(12) 0.0034(12)
C15 0.059(2) 0.075(3) 0.0389(18) -0.0013(16) 0.0106(15) 0.0191(18)
C16 0.084(3) 0.050(2) 0.057(2) -0.0026(17) 0.032(2) 0.0268(19)
C17 0.0608(19) 0.0432(16) 0.0357(15) 0.0042(12) 0.0118(13) 0.0283(14)
C18 0.064(2) 0.0358(15) 0.0447(18) -0.0018(13) 0.0040(15) 0.0194(14)
C19 0.0466(16) 0.0417(16) 0.0387(16) 0.0103(13) 0.0002(13) 0.0105(13)
C20 0.059(2) 0.0464(19) 0.060(2) 0.0116(17) -0.0011(18) 0.0005(16)
C21A 0.041(4) 0.098(6) 0.050(4) 0.018(4) 0.017(3) 0.002(4)
C21B 0.104(7) 0.072(6) 0.041(4) -0.005(4) 0.012(4) 0.028(5)
C22 0.080(3) 0.104(4) 0.063(3) 0.011(3) 0.028(2) 0.024(3)
C23A 0.050(4) 0.068(5) 0.039(4) -0.011(3) -0.005(3) 0.015(3)
C23B 0.069(5) 0.049(4) 0.079(6) -0.026(4) -0.017(4) 0.010(4)
C24 0.098(3) 0.075(3) 0.071(3) -0.030(2) -0.001(3) 0.032(3)
C25A 0.059(4) 0.056(4) 0.070(5) -0.010(4) 0.022(4) 0.027(3)
C25B 0.060(4) 0.070(5) 0.057(5) 0.005(4) -0.007(4) 0.038(4)
C26 0.082(3) 0.063(2) 0.070(3) 0.013(2) 0.012(2) 0.037(2)
F1 0.0510(14) 0.204(4) 0.0668(17) 0.042(2) 0.0193(12) 0.0000(17)
F2 0.0745(18) 0.233(4) 0.0580(17) 0.072(2) 0.0256(14) 0.040(2)
F3 0.112(3) 0.196(4) 0.135(3) 0.026(3) 0.073(2) 0.091(3)
F4 0.0498(13) 0.199(3) 0.0591(16) -0.0011(18) 0.0003(11) 0.0533(18)
F5 0.077(2) 0.194(5) 0.302(7) -0.194(6) -0.061(3) 0.023(3)
F6 0.0720(19) 0.344(7) 0.0410(16) 0.001(2) -0.0063(14) 0.071(3)
F7 0.114(2) 0.202(3) 0.0429(13) -0.0471(17) -0.0259(13) 0.108(2)
F8 0.0318(9) 0.0859(15) 0.0647(14) 0.0060(11) 0.0015(9) 0.0146(9)
F9 0.0713(16) 0.119(2) 0.0735(18) 0.0544(17) -0.0266(13) -0.0149(15)
F10A 0.142(6) 0.049(3) 0.074(4) -0.020(3) -0.009(4) 0.051(4)
F10B 0.253(13) 0.111(7) 0.106(7) 0.042(6) 0.101(9) 0.124(9)
F11A 0.085(5) 0.081(5) 0.148(8) 0.035(7) 0.032(6) 0.058(4)
F11B 0.176(11) 0.063(5) 0.175(10) -0.010(6) -0.075(9) 0.077(6)
F12A 0.241(15) 0.049(4) 0.060(4) 0.031(3) 0.066(6) 0.070(6)
F12B 0.119(7) 0.073(6) 0.34(2) 0.103(9) 0.121(11) 0.046(5)
F13 0.116(2) 0.117(2) 0.105(2) 0.0235(19) 0.0267(19) 0.081(2)
F14 0.161(4) 0.167(4) 0.548(12) 0.261(6) 0.215(6) 0.120(3)
F15 0.170(4) 0.177(4) 0.101(3) -0.017(2) -0.040(3) 0.128(3)
F16 0.0702(15) 0.1056(19) 0.0620(15) -0.0076(13) 0.0280(12) 0.0328(14)
134

F17 0.1000(19) 0.0595(14) 0.0672(16) -0.0178(11) 0.0150(14) 0.0146(13)

F18 0.119(2) 0.111(2) 0.0332(12) 0.0058(12) 0.0153(13) 0.0527(18)
F19A 0.070(3) 0.097(5) 0.094(5) 0.009(4) 0.050(3) 0.035(3)
F19B 0.160(10) 0.227(15) 0.094(8) -0.064(8) 0.086(7) -0.039(9)
F20A 0.111(5) 0.066(5) 0.065(4) -0.034(4) 0.044(4) 0.000(4)
F20B 0.42(2) 0.115(10) 0.118(10) 0.077(8) 0.174(14) 0.196(14)
F21A 0.290(17) 0.063(4) 0.051(5) 0.038(4) 0.093(8) 0.107(7)
F21B 0.256(15) 0.304(17) 0.039(4) 0.047(7) 0.051(6) 0.214(14)
F22A 0.118(9) 0.087(6) 0.119(7) -0.023(6) 0.083(7) -0.030(6)
F22B 0.063(5) 0.062(5) 0.274(17) 0.038(9) 0.066(9) 0.012(4)
F23A 0.106(6) 0.075(5) 0.186(14) 0.084(7) 0.060(7) 0.045(5)
F23B 0.122(9) 0.101(8) 0.063(4) 0.055(5) -0.043(5) -0.046(7)
F24A 0.108(8) 0.168(15) 0.049(5) 0.041(7) -0.046(5) -0.088(9)
F24B 0.172(14) 0.066(5) 0.121(12) -0.032(6) 0.027(9) -0.049(6)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O3 1.942(2) . ?
Cu1 O2 1.952(2) . ?
Cu1 O1 1.975(2) . ?
Cu1 O4 1.9756(19) . ?
Cu1 O5 2.204(2) . ?
Cu1 Cu2 3.0449(5) . ?
Cu2 O7 1.934(2) . ?
Cu2 O8 1.955(2) . ?
Cu2 O1 1.960(2) . ?
Cu2 O6 1.961(2) . ?
Cu2 O9 2.208(2) . ?
O1 H1OH 0.8342 . ?
O2 C2 1.245(4) . ?
135

O3 C4 1.269(4) . ?
O4 C7 1.260(4) . ?
O5 C9 1.235(4) . ?
O6 C12 1.250(4) . ?
O7 C14 1.256(4) . ?
O8 C17 1.263(4) . ?
O9 C19 1.217(4) . ?
N1 C25B 1.439(8) . ?
N1 C21A 1.458(8) . ?
N1 C23B 1.556(8) . ?
N1 C23A 1.563(7) . ?
N1 C21B 1.584(9) . ?
N1 C25A 1.588(8) . ?
N1 H1N 0.9703 . ?
C1 F1 1.311(6) . ?
C1 F2 1.326(5) . ?
C1 F3 1.329(7) . ?
C1 C2 1.530(5) . ?
C2 C3 1.373(5) . ?
C3 C4 1.377(5) . ?
C3 H3 0.9500 . ?
C4 C5 1.538(5) . ?
C5 F5 1.258(8) . ?
C5 F4 1.306(5) . ?
C5 F6 1.394(8) . ?
C6 F7 1.304(4) . ?
C6 F9 1.312(4) . ?
C6 F8 1.313(4) . ?
C6 C7 1.548(4) . ?
C7 C8 1.369(4) . ?
C8 C9 1.400(4) . ?
C8 H8 0.9500 . ?
C9 C10 1.535(5) . ?
C10 F11A 1.267(8) . ?
C10 F12A 1.274(8) . ?
C10 F12B 1.275(9) . ?
C10 F10B 1.299(8) . ?
C10 F10A 1.318(7) . ?
C10 F11B 1.348(9) . ?
C11 F14 1.223(5) . ?
C11 F15 1.309(6) . ?
C11 F13 1.310(5) . ?
C11 C12 1.532(5) . ?
C12 C13 1.400(5) . ?
136

C13 C14 1.382(5) . ?

C13 H13 0.9500 . ?
C14 C15 1.540(5) . ?
C15 F16 1.301(5) . ?
C15 F18 1.322(4) . ?
C15 F17 1.336(5) . ?
C16 F20B 1.194(9) . ?
C16 F21A 1.201(7) . ?
C16 F20A 1.314(8) . ?
C16 F19B 1.323(11) . ?
C16 F19A 1.351(7) . ?
C16 F21B 1.352(11) . ?
C16 C17 1.520(4) . ?
C17 C18 1.373(5) . ?
C18 C19 1.414(5) . ?
C18 H18 0.9500 . ?
C19 C20 1.555(5) . ?
C20 F22B 1.211(10) . ?
C20 F23B 1.240(9) . ?
C20 F24A 1.251(11) . ?
C20 F24B 1.304(14) . ?
C20 F23A 1.315(11) . ?
C20 F22A 1.341(11) . ?
C21A C21B 1.234(12) . ?
C21A C23B 1.449(12) . ?
C21A C22 1.603(10) . ?
C21B C22 1.377(11) . ?
C21B C25A 1.813(13) . ?
C23A C25B 1.466(11) . ?
C23A C24 1.600(9) . ?
C23A C23B 1.612(13) . ?
C23B C24 1.553(11) . ?
C25A C25B 1.181(11) . ?
C25A C26 1.388(10) . ?
C25B C26 1.586(10) . ?
F10A F10B 1.119(14) . ?
F10A F12B 1.369(17) . ?
F10B F11A 1.241(15) . ?
F11A F11B 1.039(15) . ?
F11B F12A 1.475(16) . ?
F12A F12B 0.946(17) . ?
F19A F19B 1.27(2) . ?
F19A F20B 1.34(2) . ?
F19B F21A 1.141(16) . ?
137

F20A F20B 0.84(2) . ?

F20A F21B 1.606(17) . ?
F21A F21B 1.019(17) . ?
F22A F22B 0.812(19) . ?
F22A F23B 1.678(19) . ?
F22B F24A 1.56(2) . ?
F23A F23B 0.52(3) . ?
F23A F24B 1.75(2) . ?
F24A F24B 0.60(3) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 Cu1 O2 92.08(9) . . ?
O3 Cu1 O1 91.08(9) . . ?
O2 Cu1 O1 166.30(9) . . ?
O3 Cu1 O4 177.50(9) . . ?
O2 Cu1 O4 89.27(9) . . ?
O1 Cu1 O4 87.12(8) . . ?
O3 Cu1 O5 93.28(9) . . ?
O2 Cu1 O5 92.46(9) . . ?
O1 Cu1 O5 100.67(9) . . ?
O4 Cu1 O5 88.76(8) . . ?
O3 Cu1 Cu2 109.07(7) . . ?
O2 Cu1 Cu2 127.61(6) . . ?
O1 Cu1 Cu2 39.13(6) . . ?
O4 Cu1 Cu2 68.46(6) . . ?
O5 Cu1 Cu2 131.49(6) . . ?
O7 Cu2 O8 170.40(9) . . ?
O7 Cu2 O1 88.97(9) . . ?
O8 Cu2 O1 87.89(9) . . ?
O7 Cu2 O6 92.22(9) . . ?
O8 Cu2 O6 89.11(9) . . ?
O1 Cu2 O6 168.63(9) . . ?
O7 Cu2 O9 100.31(9) . . ?
O8 Cu2 O9 89.19(9) . . ?
O1 Cu2 O9 100.49(9) . . ?
O6 Cu2 O9 90.43(10) . . ?
O7 Cu2 Cu1 114.16(7) . . ?
138

O8 Cu2 Cu1 58.61(6) . . ?

O1 Cu2 Cu1 39.48(6) . . ?
O6 Cu2 Cu1 130.91(7) . . ?
O9 Cu2 Cu1 121.67(7) . . ?
Cu2 O1 Cu1 101.40(8) . . ?
Cu2 O1 H1OH 99.9 . . ?
Cu1 O1 H1OH 103.5 . . ?
C2 O2 Cu1 123.6(2) . . ?
C4 O3 Cu1 122.8(2) . . ?
C7 O4 Cu1 124.63(18) . . ?
C9 O5 Cu1 121.10(19) . . ?
C12 O6 Cu2 124.2(2) . . ?
C14 O7 Cu2 124.9(2) . . ?
C17 O8 Cu2 126.7(2) . . ?
C19 O9 Cu2 121.3(2) . . ?
C25B N1 C21A 134.9(5) . . ?
C25B N1 C23B 116.0(5) . . ?
C21A N1 C23B 57.4(6) . . ?
C25B N1 C23A 58.3(5) . . ?
C21A N1 C23A 114.0(5) . . ?
C23B N1 C23A 62.2(5) . . ?
C25B N1 C21B 110.5(5) . . ?
C21A N1 C21B 47.7(5) . . ?
C23B N1 C21B 104.6(6) . . ?
C23A N1 C21B 145.5(5) . . ?
C25B N1 C25A 45.6(4) . . ?
C21A N1 C25A 112.8(5) . . ?
C23B N1 C25A 147.5(5) . . ?
C23A N1 C25A 103.5(5) . . ?
C21B N1 C25A 69.7(5) . . ?
C25B N1 H1N 110.2 . . ?
C21A N1 H1N 114.0 . . ?
C23B N1 H1N 107.8 . . ?
C23A N1 H1N 107.2 . . ?
C21B N1 H1N 107.3 . . ?
C25A N1 H1N 104.3 . . ?
F1 C1 F2 107.1(4) . . ?
F1 C1 F3 104.4(4) . . ?
F2 C1 F3 109.9(4) . . ?
F1 C1 C2 112.5(4) . . ?
F2 C1 C2 112.5(4) . . ?
F3 C1 C2 110.1(4) . . ?
O2 C2 C3 129.1(3) . . ?
O2 C2 C1 114.1(3) . . ?
139

C3 C2 C1 116.8(3) . . ?
C2 C3 C4 120.5(3) . . ?
C2 C3 H3 119.7 . . ?
C4 C3 H3 119.7 . . ?
O3 C4 C3 129.0(3) . . ?
O3 C4 C5 113.1(3) . . ?
C3 C4 C5 117.7(3) . . ?
F5 C5 F4 109.9(6) . . ?
F5 C5 F6 109.9(5) . . ?
F4 C5 F6 104.0(5) . . ?
F5 C5 C4 111.0(5) . . ?
F4 C5 C4 112.6(4) . . ?
F6 C5 C4 109.2(5) . . ?
F7 C6 F9 108.2(3) . . ?
F7 C6 F8 105.9(3) . . ?
F9 C6 F8 105.7(3) . . ?
F7 C6 C7 113.7(3) . . ?
F9 C6 C7 112.0(3) . . ?
F8 C6 C7 111.0(3) . . ?
O4 C7 C8 130.7(3) . . ?
O4 C7 C6 112.4(3) . . ?
C8 C7 C6 116.9(3) . . ?
C7 C8 C9 123.4(3) . . ?
C7 C8 H8 118.3 . . ?
C9 C8 H8 118.3 . . ?
O5 C9 C8 128.5(3) . . ?
O5 C9 C10 113.9(3) . . ?
C8 C9 C10 117.6(3) . . ?
F11A C10 F12A 112.7(8) . . ?
F11A C10 F12B 133.3(6) . . ?
F12A C10 F12B 43.6(8) . . ?
F11A C10 F10B 57.8(7) . . ?
F12A C10 F10B 135.6(5) . . ?
F12B C10 F10B 107.4(9) . . ?
F11A C10 F10A 106.5(6) . . ?
F12A C10 F10A 106.1(7) . . ?
F12B C10 F10A 63.7(8) . . ?
F10B C10 F10A 50.7(7) . . ?
F11A C10 F11B 46.7(7) . . ?
F12A C10 F11B 68.4(8) . . ?
F12B C10 F11B 105.0(9) . . ?
F10B C10 F11B 99.8(8) . . ?
F10A C10 F11B 133.9(5) . . ?
F11A C10 C9 110.0(4) . . ?
140

F12A C10 C9 109.3(4) . . ?

F12B C10 C9 115.9(5) . . ?
F10B C10 C9 114.6(5) . . ?
F10A C10 C9 112.2(4) . . ?
F11B C10 C9 112.5(4) . . ?
F14 C11 F15 110.9(5) . . ?
F14 C11 F13 107.4(5) . . ?
F15 C11 F13 99.7(4) . . ?
F14 C11 C12 112.3(4) . . ?
F15 C11 C12 112.9(4) . . ?
F13 C11 C12 112.9(3) . . ?
O6 C12 C13 128.3(3) . . ?
O6 C12 C11 115.1(3) . . ?
C13 C12 C11 116.6(3) . . ?
C14 C13 C12 120.9(3) . . ?
C14 C13 H13 119.6 . . ?
C12 C13 H13 119.6 . . ?
O7 C14 C13 128.6(3) . . ?
O7 C14 C15 112.7(3) . . ?
C13 C14 C15 118.7(3) . . ?
F16 C15 F18 109.0(3) . . ?
F16 C15 F17 107.9(3) . . ?
F18 C15 F17 105.7(3) . . ?
F16 C15 C14 111.0(3) . . ?
F18 C15 C14 113.2(3) . . ?
F17 C15 C14 109.7(3) . . ?
F20B C16 F21A 126.3(6) . . ?
F20B C16 F20A 38.8(11) . . ?
F21A C16 F20A 114.2(8) . . ?
F20B C16 F19B 106.0(10) . . ?
F21A C16 F19B 53.5(9) . . ?
F20A C16 F19B 132.6(6) . . ?
F20B C16 F19A 62.9(10) . . ?
F21A C16 F19A 108.5(8) . . ?
F20A C16 F19A 101.7(5) . . ?
F19B C16 F19A 56.5(9) . . ?
F20B C16 F21B 105.4(10) . . ?
F21A C16 F21B 46.6(8) . . ?
F20A C16 F21B 74.1(9) . . ?
F19B C16 F21B 97.9(10) . . ?
F19A C16 F21B 141.9(7) . . ?
F20B C16 C17 120.0(6) . . ?
F21A C16 C17 113.4(4) . . ?
F20A C16 C17 111.9(5) . . ?
141

F19B C16 C17 114.5(5) . . ?

F19A C16 C17 106.2(4) . . ?
F21B C16 C17 110.5(6) . . ?
O8 C17 C18 129.3(3) . . ?
O8 C17 C16 113.2(3) . . ?
C18 C17 C16 117.6(3) . . ?
C17 C18 C19 124.1(3) . . ?
C17 C18 H18 117.9 . . ?
C19 C18 H18 117.9 . . ?
O9 C19 C18 128.2(3) . . ?
O9 C19 C20 114.5(3) . . ?
C18 C19 C20 117.3(3) . . ?
F22B C20 F23B 111.9(10) . . ?
F22B C20 F24A 78.4(12) . . ?
F23B C20 F24A 121.3(9) . . ?
F22B C20 F24B 103.3(11) . . ?
F23B C20 F24B 101.4(10) . . ?
F24A C20 F24B 27.2(15) . . ?
F22B C20 F23A 131.7(10) . . ?
F23B C20 F23A 23.5(12) . . ?
F24A C20 F23A 108.3(11) . . ?
F24B C20 F23A 83.6(11) . . ?
F22B C20 F22A 36.6(9) . . ?
F23B C20 F22A 81.0(10) . . ?
F24A C20 F22A 111.3(11) . . ?
F24B C20 F22A 130.3(10) . . ?
F23A C20 F22A 104.2(9) . . ?
F22B C20 C19 112.3(6) . . ?
F23B C20 C19 113.7(6) . . ?
F24A C20 C19 114.0(7) . . ?
F24B C20 C19 113.3(9) . . ?
F23A C20 C19 108.0(7) . . ?
F22A C20 C19 110.5(6) . . ?
C21B C21A C23B 135.5(9) . . ?
C21B C21A N1 71.5(6) . . ?
C23B C21A N1 64.7(5) . . ?
C21B C21A C22 56.3(6) . . ?
C23B C21A C22 149.4(8) . . ?
N1 C21A C22 110.7(5) . . ?
C21A C21B C22 75.5(7) . . ?
C21A C21B N1 60.8(5) . . ?
C22 C21B N1 116.4(7) . . ?
C21A C21B C25A 111.4(7) . . ?
C22 C21B C25A 155.4(8) . . ?
142

N1 C21B C25A 55.2(4) . . ?

C21B C22 C21A 48.2(5) . . ?
C25B C23A N1 56.6(4) . . ?
C25B C23A C24 158.8(6) . . ?
N1 C23A C24 104.8(5) . . ?
C25B C23A C23B 111.1(6) . . ?
N1 C23A C23B 58.7(4) . . ?
C24 C23A C23B 57.8(5) . . ?
C21A C23B C24 162.8(8) . . ?
C21A C23B N1 57.9(4) . . ?
C24 C23B N1 107.5(7) . . ?
C21A C23B C23A 111.6(7) . . ?
C24 C23B C23A 60.7(5) . . ?
N1 C23B C23A 59.1(4) . . ?
C23B C24 C23A 61.5(5) . . ?
C25B C25A C26 75.7(7) . . ?
C25B C25A N1 60.5(5) . . ?
C26 C25A N1 114.8(5) . . ?
C25B C25A C21B 110.4(7) . . ?
C26 C25A C21B 154.5(7) . . ?
N1 C25A C21B 55.0(4) . . ?
C25A C25B N1 73.9(6) . . ?
C25A C25B C23A 138.1(8) . . ?
N1 C25B C23A 65.1(5) . . ?
C25A C25B C26 58.0(6) . . ?
N1 C25B C26 112.1(5) . . ?
C23A C25B C26 147.1(7) . . ?
C25A C26 C25B 46.2(5) . . ?
F10B F10A C10 63.8(6) . . ?
F10B F10A F12B 112.6(10) . . ?
C10 F10A F12B 56.6(6) . . ?
F10A F10B F11A 122.6(9) . . ?
F10A F10B C10 65.5(6) . . ?
F11A F10B C10 59.8(6) . . ?
F11B F11A F10B 125.0(13) . . ?
F11B F11A C10 70.8(8) . . ?
F10B F11A C10 62.4(6) . . ?
F11A F11B C10 62.5(7) . . ?
F11A F11B F12A 113.4(10) . . ?
C10 F11B F12A 53.4(5) . . ?
F12B F12A C10 68.2(8) . . ?
F12B F12A F11B 116.8(11) . . ?
C10 F12A F11B 58.2(6) . . ?
F12A F12B C10 68.2(8) . . ?
143

F12A F12B F10A 126.0(12) . . ?

C10 F12B F10A 59.7(6) . . ?
F19B F19A F20B 101.2(8) . . ?
F19B F19A C16 60.6(6) . . ?
F20B F19A C16 52.8(5) . . ?
F21A F19B F19A 118.8(11) . . ?
F21A F19B C16 57.8(6) . . ?
F19A F19B C16 62.9(8) . . ?
F20B F20A C16 62.9(9) . . ?
F20B F20A F21B 107.8(13) . . ?
C16 F20A F21B 54.0(6) . . ?
F20A F20B C16 78.4(11) . . ?
F20A F20B F19A 142.6(12) . . ?
C16 F20B F19A 64.3(8) . . ?
F21B F21A F19B 138.0(13) . . ?
F21B F21A C16 74.5(8) . . ?
F19B F21A C16 68.7(8) . . ?
F21A F21B C16 58.9(7) . . ?
F21A F21B F20A 105.0(10) . . ?
C16 F21B F20A 51.9(5) . . ?
F22B F22A C20 63.0(10) . . ?
F22B F22A F23B 103.9(14) . . ?
C20 F22A F23B 46.9(6) . . ?
F22A F22B C20 80.4(15) . . ?
F22A F22B F24A 126.4(18) . . ?
C20 F22B F24A 51.9(7) . . ?
F23B F23A C20 70.3(18) . . ?
F23B F23A F24B 108(2) . . ?
C20 F23A F24B 47.9(7) . . ?
F23A F23B C20 86(2) . . ?
F23A F23B F22A 138(2) . . ?
C20 F23B F22A 52.1(6) . . ?
F24B F24A C20 81.3(18) . . ?
F24B F24A F22B 126(2) . . ?
C20 F24A F22B 49.7(8) . . ?
F24A F24B C20 72(2) . . ?
F24A F24B F23A 116(3) . . ?
C20 F24B F23A 48.5(6) . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
144

_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O3 Cu1 Cu2 O7 -121.68(10) . . . . ?
O2 Cu1 Cu2 O7 129.96(11) . . . . ?
O1 Cu1 Cu2 O7 -54.86(12) . . . . ?
O4 Cu1 Cu2 O7 58.71(9) . . . . ?
O5 Cu1 Cu2 O7 -8.94(11) . . . . ?
O3 Cu1 Cu2 O8 65.47(11) . . . . ?
O2 Cu1 Cu2 O8 -42.88(12) . . . . ?
O1 Cu1 Cu2 O8 132.30(12) . . . . ?
O4 Cu1 Cu2 O8 -114.14(10) . . . . ?
O5 Cu1 Cu2 O8 178.22(11) . . . . ?
O3 Cu1 Cu2 O1 -66.82(11) . . . . ?
O2 Cu1 Cu2 O1 -175.18(12) . . . . ?
O4 Cu1 Cu2 O1 113.57(11) . . . . ?
O5 Cu1 Cu2 O1 45.92(12) . . . . ?
O3 Cu1 Cu2 O6 121.91(11) . . . . ?
O2 Cu1 Cu2 O6 13.55(13) . . . . ?
O1 Cu1 Cu2 O6 -171.27(13) . . . . ?
O4 Cu1 Cu2 O6 -57.70(11) . . . . ?
O5 Cu1 Cu2 O6 -125.35(12) . . . . ?
O3 Cu1 Cu2 O9 -1.20(10) . . . . ?
O2 Cu1 Cu2 O9 -109.55(12) . . . . ?
O1 Cu1 Cu2 O9 65.63(12) . . . . ?
O4 Cu1 Cu2 O9 179.19(10) . . . . ?
O5 Cu1 Cu2 O9 111.55(11) . . . . ?
O7 Cu2 O1 Cu1 131.74(10) . . . . ?
O8 Cu2 O1 Cu1 -39.19(9) . . . . ?
O6 Cu2 O1 Cu1 35.6(5) . . . . ?
O9 Cu2 O1 Cu1 -127.97(9) . . . . ?
O3 Cu1 O1 Cu2 119.66(10) . . . . ?
O2 Cu1 O1 Cu2 16.3(4) . . . . ?
O4 Cu1 O1 Cu2 -58.61(9) . . . . ?
O5 Cu1 O1 Cu2 -146.80(9) . . . . ?
O3 Cu1 O2 C2 15.5(3) . . . . ?
O1 Cu1 O2 C2 118.7(4) . . . . ?
O4 Cu1 O2 C2 -166.6(3) . . . . ?
O5 Cu1 O2 C2 -77.9(3) . . . . ?
Cu2 Cu1 O2 C2 131.7(2) . . . . ?
O2 Cu1 O3 C4 -16.0(3) . . . . ?
145

O1 Cu1 O3 C4 177.3(3) . . . . ?
O4 Cu1 O3 C4 -138.9(19) . . . . ?
O5 Cu1 O3 C4 76.6(3) . . . . ?
Cu2 Cu1 O3 C4 -147.2(2) . . . . ?
O3 Cu1 O4 C7 -126.7(19) . . . . ?
O2 Cu1 O4 C7 110.4(2) . . . . ?
O1 Cu1 O4 C7 -82.9(2) . . . . ?
O5 Cu1 O4 C7 17.9(2) . . . . ?
Cu2 Cu1 O4 C7 -118.2(2) . . . . ?
O3 Cu1 O5 C9 163.6(2) . . . . ?
O2 Cu1 O5 C9 -104.1(2) . . . . ?
O1 Cu1 O5 C9 71.9(2) . . . . ?
O4 Cu1 O5 C9 -14.9(2) . . . . ?
Cu2 Cu1 O5 C9 44.4(3) . . . . ?
O7 Cu2 O6 C12 9.8(3) . . . . ?
O8 Cu2 O6 C12 -179.7(3) . . . . ?
O1 Cu2 O6 C12 105.6(5) . . . . ?
O9 Cu2 O6 C12 -90.5(3) . . . . ?
Cu1 Cu2 O6 C12 135.0(2) . . . . ?
O8 Cu2 O7 C14 -107.0(6) . . . . ?
O1 Cu2 O7 C14 -177.9(2) . . . . ?
O6 Cu2 O7 C14 -9.2(2) . . . . ?
O9 Cu2 O7 C14 81.6(2) . . . . ?
Cu1 Cu2 O7 C14 -146.6(2) . . . . ?
O7 Cu2 O8 C17 179.4(5) . . . . ?
O1 Cu2 O8 C17 -109.6(3) . . . . ?
O6 Cu2 O8 C17 81.4(3) . . . . ?
O9 Cu2 O8 C17 -9.1(3) . . . . ?
Cu1 Cu2 O8 C17 -137.7(3) . . . . ?
O7 Cu2 O9 C19 -170.0(2) . . . . ?
O8 Cu2 O9 C19 11.5(3) . . . . ?
O1 Cu2 O9 C19 99.2(3) . . . . ?
O6 Cu2 O9 C19 -77.6(3) . . . . ?
Cu1 Cu2 O9 C19 63.1(3) . . . . ?
Cu1 O2 C2 C3 -6.8(5) . . . . ?
Cu1 O2 C2 C1 176.2(3) . . . . ?
F1 C1 C2 O2 -32.8(6) . . . . ?
F2 C1 C2 O2 -153.9(4) . . . . ?
F3 C1 C2 O2 83.2(5) . . . . ?
F1 C1 C2 C3 149.8(4) . . . . ?
F2 C1 C2 C3 28.7(6) . . . . ?
F3 C1 C2 C3 -94.3(4) . . . . ?
O2 C2 C3 C4 -7.4(6) . . . . ?
C1 C2 C3 C4 169.6(4) . . . . ?
146

Cu1 O3 C4 C3 8.2(5) . . . . ?
Cu1 O3 C4 C5 -175.8(3) . . . . ?
C2 C3 C4 O3 6.6(6) . . . . ?
C2 C3 C4 C5 -169.2(4) . . . . ?
O3 C4 C5 F5 -81.7(6) . . . . ?
C3 C4 C5 F5 94.8(6) . . . . ?
O3 C4 C5 F4 42.0(7) . . . . ?
C3 C4 C5 F4 -141.6(5) . . . . ?
O3 C4 C5 F6 157.0(4) . . . . ?
C3 C4 C5 F6 -26.6(6) . . . . ?
Cu1 O4 C7 C8 -14.6(4) . . . . ?
Cu1 O4 C7 C6 167.70(18) . . . . ?
F7 C6 C7 O4 -158.8(3) . . . . ?
F9 C6 C7 O4 -35.9(4) . . . . ?
F8 C6 C7 O4 81.9(3) . . . . ?
F7 C6 C7 C8 23.2(4) . . . . ?
F9 C6 C7 C8 146.1(3) . . . . ?
F8 C6 C7 C8 -96.1(3) . . . . ?
O4 C7 C8 C9 -0.2(5) . . . . ?
C6 C7 C8 C9 177.4(3) . . . . ?
Cu1 O5 C9 C8 7.5(5) . . . . ?
Cu1 O5 C9 C10 -173.1(2) . . . . ?
C7 C8 C9 O5 3.3(6) . . . . ?
C7 C8 C9 C10 -176.1(3) . . . . ?
O5 C9 C10 F11A 63.1(8) . . . . ?
C8 C9 C10 F11A -117.4(8) . . . . ?
O5 C9 C10 F12A -61.1(9) . . . . ?
C8 C9 C10 F12A 118.4(8) . . . . ?
O5 C9 C10 F12B -108.0(13) . . . . ?
C8 C9 C10 F12B 71.4(13) . . . . ?
O5 C9 C10 F10B 125.9(11) . . . . ?
C8 C9 C10 F10B -54.6(12) . . . . ?
O5 C9 C10 F10A -178.5(7) . . . . ?
C8 C9 C10 F10A 0.9(8) . . . . ?
O5 C9 C10 F11B 12.8(12) . . . . ?
C8 C9 C10 F11B -167.7(12) . . . . ?
Cu2 O6 C12 C13 -6.4(5) . . . . ?
Cu2 O6 C12 C11 172.8(2) . . . . ?
F14 C11 C12 O6 -101.2(6) . . . . ?
F15 C11 C12 O6 132.5(4) . . . . ?
F13 C11 C12 O6 20.4(5) . . . . ?
F14 C11 C12 C13 78.1(6) . . . . ?
F15 C11 C12 C13 -48.2(5) . . . . ?
F13 C11 C12 C13 -160.3(4) . . . . ?
147

O6 C12 C13 C14 -1.5(5) . . . . ?

C11 C12 C13 C14 179.3(3) . . . . ?
Cu2 O7 C14 C13 5.1(5) . . . . ?
Cu2 O7 C14 C15 -175.4(2) . . . . ?
C12 C13 C14 O7 2.3(5) . . . . ?
C12 C13 C14 C15 -177.2(3) . . . . ?
O7 C14 C15 F16 54.4(4) . . . . ?
C13 C14 C15 F16 -126.0(3) . . . . ?
O7 C14 C15 F18 177.4(3) . . . . ?
C13 C14 C15 F18 -3.0(5) . . . . ?
O7 C14 C15 F17 -64.7(4) . . . . ?
C13 C14 C15 F17 114.8(4) . . . . ?
Cu2 O8 C17 C18 4.3(5) . . . . ?
Cu2 O8 C17 C16 -176.4(2) . . . . ?
F20B C16 C17 O8 137.5(14) . . . . ?
F21A C16 C17 O8 -49.3(10) . . . . ?
F20A C16 C17 O8 179.9(6) . . . . ?
F19B C16 C17 O8 9.7(13) . . . . ?
F19A C16 C17 O8 69.8(6) . . . . ?
F21B C16 C17 O8 -99.7(10) . . . . ?
F20B C16 C17 C18 -43.1(15) . . . . ?
F21A C16 C17 C18 130.1(10) . . . . ?
F20A C16 C17 C18 -0.7(7) . . . . ?
F19B C16 C17 C18 -170.9(13) . . . . ?
F19A C16 C17 C18 -110.8(5) . . . . ?
F21B C16 C17 C18 79.7(10) . . . . ?
O8 C17 C18 C19 2.9(6) . . . . ?
C16 C17 C18 C19 -176.4(3) . . . . ?
Cu2 O9 C19 C18 -9.5(5) . . . . ?
Cu2 O9 C19 C20 171.0(2) . . . . ?
C17 C18 C19 O9 0.9(6) . . . . ?
C17 C18 C19 C20 -179.6(3) . . . . ?
O9 C19 C20 F22B 58.1(12) . . . . ?
C18 C19 C20 F22B -121.5(11) . . . . ?
O9 C19 C20 F23B -70.2(11) . . . . ?
C18 C19 C20 F23B 110.1(10) . . . . ?
O9 C19 C20 F24A 145.0(13) . . . . ?
C18 C19 C20 F24A -34.6(13) . . . . ?
O9 C19 C20 F24B 174.7(10) . . . . ?
C18 C19 C20 F24B -4.9(11) . . . . ?
O9 C19 C20 F23A -94.6(8) . . . . ?
C18 C19 C20 F23A 85.8(8) . . . . ?
O9 C19 C20 F22A 18.7(9) . . . . ?
C18 C19 C20 F22A -160.9(8) . . . . ?
148

C25B N1 C21A C21B -76.2(9) . . . . ?

C23B N1 C21A C21B -171.7(9) . . . . ?
C23A N1 C21A C21B -144.6(7) . . . . ?
C25A N1 C21A C21B -26.9(8) . . . . ?
C25B N1 C21A C23B 95.5(8) . . . . ?
C23A N1 C21A C23B 27.1(7) . . . . ?
C21B N1 C21A C23B 171.7(9) . . . . ?
C25A N1 C21A C23B 144.8(6) . . . . ?
C25B N1 C21A C22 -117.5(7) . . . . ?
C23B N1 C21A C22 147.0(9) . . . . ?
C23A N1 C21A C22 174.1(5) . . . . ?
C21B N1 C21A C22 -41.3(7) . . . . ?
C25A N1 C21A C22 -68.2(7) . . . . ?
C23B C21A C21B C22 -142.8(11) . . . . ?
N1 C21A C21B C22 -132.1(6) . . . . ?
C23B C21A C21B N1 -10.7(11) . . . . ?
C22 C21A C21B N1 132.1(6) . . . . ?
C23B C21A C21B C25A 12.3(16) . . . . ?
N1 C21A C21B C25A 23.1(6) . . . . ?
C22 C21A C21B C25A 155.2(9) . . . . ?
C25B N1 C21B C21A 132.7(7) . . . . ?
C23B N1 C21B C21A 7.2(7) . . . . ?
C23A N1 C21B C21A 69.2(11) . . . . ?
C25A N1 C21B C21A 153.6(8) . . . . ?
C25B N1 C21B C22 -173.9(7) . . . . ?
C21A N1 C21B C22 53.3(7) . . . . ?
C23B N1 C21B C22 60.5(9) . . . . ?
C23A N1 C21B C22 122.5(9) . . . . ?
C25A N1 C21B C22 -153.1(9) . . . . ?
C25B N1 C21B C25A -20.9(6) . . . . ?
C21A N1 C21B C25A -153.6(8) . . . . ?
C23B N1 C21B C25A -146.4(5) . . . . ?
C23A N1 C21B C25A -84.4(9) . . . . ?
N1 C21B C22 C21A -46.3(6) . . . . ?
C25A C21B C22 C21A -109.9(17) . . . . ?
C23B C21A C22 C21B 123.8(16) . . . . ?
N1 C21A C22 C21B 48.8(7) . . . . ?
C21A N1 C23A C25B 129.3(6) . . . . ?
C23B N1 C23A C25B 155.0(7) . . . . ?
C21B N1 C23A C25B 80.2(9) . . . . ?
C25A N1 C23A C25B 6.4(6) . . . . ?
C25B N1 C23A C24 168.7(7) . . . . ?
C21A N1 C23A C24 -62.0(7) . . . . ?
C23B N1 C23A C24 -36.3(5) . . . . ?
149

C21B N1 C23A C24 -111.1(9) . . . . ?

C25A N1 C23A C24 175.1(5) . . . . ?
C25B N1 C23A C23B -155.0(7) . . . . ?
C21A N1 C23A C23B -25.7(7) . . . . ?
C21B N1 C23A C23B -74.8(10) . . . . ?
C25A N1 C23A C23B -148.6(6) . . . . ?
C21B C21A C23B C24 46(3) . . . . ?
N1 C21A C23B C24 34(3) . . . . ?
C22 C21A C23B C24 -54(4) . . . . ?
C21B C21A C23B N1 11.3(11) . . . . ?
C22 C21A C23B N1 -88.2(13) . . . . ?
C21B C21A C23B C23A -14.5(16) . . . . ?
N1 C21A C23B C23A -25.7(6) . . . . ?
C22 C21A C23B C23A -114.0(14) . . . . ?
C25B N1 C23B C21A -128.4(6) . . . . ?
C23A N1 C23B C21A -151.9(7) . . . . ?
C21B N1 C23B C21A -6.3(7) . . . . ?
C25A N1 C23B C21A -81.5(11) . . . . ?
C25B N1 C23B C24 61.7(7) . . . . ?
C21A N1 C23B C24 -169.9(8) . . . . ?
C23A N1 C23B C24 38.2(5) . . . . ?
C21B N1 C23B C24 -176.2(6) . . . . ?
C25A N1 C23B C24 108.6(10) . . . . ?
C25B N1 C23B C23A 23.6(6) . . . . ?
C21A N1 C23B C23A 151.9(7) . . . . ?
C21B N1 C23B C23A 145.6(6) . . . . ?
C25A N1 C23B C23A 70.5(11) . . . . ?
C25B C23A C23B C21A 3.2(10) . . . . ?
N1 C23A C23B C21A 25.4(6) . . . . ?
C24 C23A C23B C21A 162.9(8) . . . . ?
C25B C23A C23B C24 -159.7(7) . . . . ?
N1 C23A C23B C24 -137.5(5) . . . . ?
C25B C23A C23B N1 -22.2(5) . . . . ?
C24 C23A C23B N1 137.5(5) . . . . ?
C21A C23B C24 C23A -68(3) . . . . ?
N1 C23B C24 C23A -37.5(5) . . . . ?
C25B C23A C24 C23B 64(2) . . . . ?
N1 C23A C24 C23B 36.7(5) . . . . ?
C21A N1 C25A C25B -131.3(7) . . . . ?
C23B N1 C25A C25B -66.7(12) . . . . ?
C23A N1 C25A C25B -7.6(7) . . . . ?
C21B N1 C25A C25B -152.2(7) . . . . ?
C25B N1 C25A C26 -55.0(7) . . . . ?
C21A N1 C25A C26 173.7(6) . . . . ?
150

C23B N1 C25A C26 -121.7(10) . . . . ?

C23A N1 C25A C26 -62.6(7) . . . . ?
C21B N1 C25A C26 152.8(8) . . . . ?
C25B N1 C25A C21B 152.2(7) . . . . ?
C21A N1 C25A C21B 20.9(6) . . . . ?
C23B N1 C25A C21B 85.5(11) . . . . ?
C23A N1 C25A C21B 144.6(6) . . . . ?
C21A C21B C25A C25B 1.1(11) . . . . ?
C22 C21B C25A C25B 103.2(17) . . . . ?
N1 C21B C25A C25B 25.7(6) . . . . ?
C21A C21B C25A C26 -98.7(16) . . . . ?
C22 C21B C25A C26 3(3) . . . . ?
N1 C21B C25A C26 -74.1(14) . . . . ?
C21A C21B C25A N1 -24.6(7) . . . . ?
C22 C21B C25A N1 77.5(16) . . . . ?
C26 C25A C25B N1 129.9(5) . . . . ?
C21B C25A C25B N1 -24.1(6) . . . . ?
C26 C25A C25B C23A 141.8(11) . . . . ?
N1 C25A C25B C23A 11.9(10) . . . . ?
C21B C25A C25B C23A -12.2(14) . . . . ?
N1 C25A C25B C26 -129.9(5) . . . . ?
C21B C25A C25B C26 -154.0(7) . . . . ?
C21A N1 C25B C25A 77.9(9) . . . . ?
C23B N1 C25B C25A 146.7(7) . . . . ?
C23A N1 C25B C25A 171.3(7) . . . . ?
C21B N1 C25B C25A 27.9(7) . . . . ?
C21A N1 C25B C23A -93.4(8) . . . . ?
C23B N1 C25B C23A -24.6(7) . . . . ?
C21B N1 C25B C23A -143.4(6) . . . . ?
C25A N1 C25B C23A -171.3(7) . . . . ?
C21A N1 C25B C26 122.5(7) . . . . ?
C23B N1 C25B C26 -168.7(6) . . . . ?
C23A N1 C25B C26 -144.1(8) . . . . ?
C21B N1 C25B C26 72.5(7) . . . . ?
C25A N1 C25B C26 44.6(5) . . . . ?
N1 C23A C25B C25A -12.6(10) . . . . ?
C24 C23A C25B C25A -44(3) . . . . ?
C23B C23A C25B C25A 10.2(14) . . . . ?
C24 C23A C25B N1 -32(2) . . . . ?
C23B C23A C25B N1 22.7(6) . . . . ?
N1 C23A C25B C26 92.6(11) . . . . ?
C24 C23A C25B C26 61(3) . . . . ?
C23B C23A C25B C26 115.4(12) . . . . ?
N1 C25A C26 C25B 47.4(5) . . . . ?
151

C21B C25A C26 C25B 107.6(14) . . . . ?

N1 C25B C26 C25A -52.7(6) . . . . ?
C23A C25B C26 C25A -130.6(13) . . . . ?
F11A C10 F10A F10B 16.2(7) . . . . ?
F12A C10 F10A F10B 136.4(8) . . . . ?
F12B C10 F10A F10B 146.8(8) . . . . ?
F11B C10 F10A F10B 61.1(14) . . . . ?
C9 C10 F10A F10B -104.3(6) . . . . ?
F11A C10 F10A F12B -130.6(7) . . . . ?
F12A C10 F10A F12B -10.4(8) . . . . ?
F10B C10 F10A F12B -146.8(8) . . . . ?
F11B C10 F10A F12B -85.7(13) . . . . ?
C9 C10 F10A F12B 109.0(6) . . . . ?
C10 F10A F10B F11A -18.9(8) . . . . ?
F12B F10A F10B F11A 10.8(12) . . . . ?
F12B F10A F10B C10 29.7(6) . . . . ?
F11A C10 F10B F10A -161.6(8) . . . . ?
F12A C10 F10B F10A -71.1(15) . . . . ?
F12B C10 F10B F10A -31.0(9) . . . . ?
F11B C10 F10B F10A -140.2(8) . . . . ?
C9 C10 F10B F10A 99.4(6) . . . . ?
F12A C10 F10B F11A 90.5(14) . . . . ?
F12B C10 F10B F11A 130.7(8) . . . . ?
F10A C10 F10B F11A 161.6(8) . . . . ?
F11B C10 F10B F11A 21.5(8) . . . . ?
C9 C10 F10B F11A -99.0(6) . . . . ?
F10A F10B F11A F11B -14.9(16) . . . . ?
C10 F10B F11A F11B -34.8(9) . . . . ?
F10A F10B F11A C10 19.9(8) . . . . ?
F12A C10 F11A F11B 19.6(9) . . . . ?
F12B C10 F11A F11B 66.4(15) . . . . ?
F10B C10 F11A F11B 150.3(9) . . . . ?
F10A C10 F11A F11B 135.6(8) . . . . ?
C9 C10 F11A F11B -102.6(7) . . . . ?
F12A C10 F11A F10B -130.7(7) . . . . ?
F12B C10 F11A F10B -83.9(13) . . . . ?
F10A C10 F11A F10B -14.7(7) . . . . ?
F11B C10 F11A F10B -150.3(9) . . . . ?
C9 C10 F11A F10B 107.1(6) . . . . ?
F10B F11A F11B C10 32.4(8) . . . . ?
F10B F11A F11B F12A 15.4(14) . . . . ?
C10 F11A F11B F12A -17.0(7) . . . . ?
F12A C10 F11B F11A -160.5(9) . . . . ?
F12B C10 F11B F11A -136.3(9) . . . . ?
152

F10B C10 F11B F11A -25.2(9) . . . . ?

F10A C10 F11B F11A -68.6(14) . . . . ?
C9 C10 F11B F11A 96.8(8) . . . . ?
F11A C10 F11B F12A 160.5(9) . . . . ?
F12B C10 F11B F12A 24.2(7) . . . . ?
F10B C10 F11B F12A 135.3(6) . . . . ?
F10A C10 F11B F12A 91.9(12) . . . . ?
C9 C10 F11B F12A -102.7(5) . . . . ?
F11A C10 F12A F12B 129.7(10) . . . . ?
F10B C10 F12A F12B 63.2(17) . . . . ?
F10A C10 F12A F12B 13.5(10) . . . . ?
F11B C10 F12A F12B 145.0(10) . . . . ?
C9 C10 F12A F12B -107.7(8) . . . . ?
F11A C10 F12A F11B -15.3(7) . . . . ?
F12B C10 F12A F11B -145.0(10) . . . . ?
F10B C10 F12A F11B -81.8(13) . . . . ?
F10A C10 F12A F11B -131.4(6) . . . . ?
C9 C10 F12A F11B 107.4(5) . . . . ?
F11A F11B F12A F12B -17.9(15) . . . . ?
C10 F11B F12A F12B -36.7(10) . . . . ?
F11A F11B F12A C10 18.8(8) . . . . ?
F11B F12A F12B C10 33.1(8) . . . . ?
C10 F12A F12B F10A -15.5(11) . . . . ?
F11B F12A F12B F10A 17.6(17) . . . . ?
F11A C10 F12B F12A -77.2(15) . . . . ?
F10B C10 F12B F12A -139.1(10) . . . . ?
F10A C10 F12B F12A -165.5(11) . . . . ?
F11B C10 F12B F12A -33.6(11) . . . . ?
C9 C10 F12B F12A 91.3(10) . . . . ?
F11A C10 F12B F10A 88.2(12) . . . . ?
F12A C10 F12B F10A 165.5(11) . . . . ?
F10B C10 F12B F10A 26.3(7) . . . . ?
F11B C10 F12B F10A 131.9(7) . . . . ?
C9 C10 F12B F10A -103.2(6) . . . . ?
F10B F10A F12B F12A -15.4(16) . . . . ?
C10 F10A F12B F12A 16.7(11) . . . . ?
F10B F10A F12B C10 -32.2(7) . . . . ?
F20B C16 F19A F19B 135.1(8) . . . . ?
F21A C16 F19A F19B 13.1(7) . . . . ?
F20A C16 F19A F19B 133.8(7) . . . . ?
F21B C16 F19A F19B 54.8(14) . . . . ?
C17 C16 F19A F19B -109.0(6) . . . . ?
F21A C16 F19A F20B -122.0(7) . . . . ?
F20A C16 F19A F20B -1.3(9) . . . . ?
153

F19B C16 F19A F20B -135.1(8) . . . . ?

F21B C16 F19A F20B -80.3(14) . . . . ?
C17 C16 F19A F20B 115.9(6) . . . . ?
F20B F19A F19B F21A 19.9(11) . . . . ?
C16 F19A F19B F21A -15.0(8) . . . . ?
F20B F19A F19B C16 35.0(6) . . . . ?
F20B C16 F19B F21A 123.6(9) . . . . ?
F20A C16 F19B F21A 90.6(15) . . . . ?
F19A C16 F19B F21A 164.4(8) . . . . ?
F21B C16 F19B F21A 15.1(8) . . . . ?
C17 C16 F19B F21A -101.8(6) . . . . ?
F20B C16 F19B F19A -40.8(8) . . . . ?
F21A C16 F19B F19A -164.4(8) . . . . ?
F20A C16 F19B F19A -73.8(13) . . . . ?
F21B C16 F19B F19A -149.4(7) . . . . ?
C17 C16 F19B F19A 93.8(7) . . . . ?
F21A C16 F20A F20B 118.4(13) . . . . ?
F19B C16 F20A F20B 56.7(19) . . . . ?
F19A C16 F20A F20B 1.8(12) . . . . ?
F21B C16 F20A F20B 142.7(14) . . . . ?
C17 C16 F20A F20B -111.2(11) . . . . ?
F20B C16 F20A F21B -142.7(14) . . . . ?
F21A C16 F20A F21B -24.3(9) . . . . ?
F19B C16 F20A F21B -86.0(14) . . . . ?
F19A C16 F20A F21B -140.9(7) . . . . ?
C17 C16 F20A F21B 106.1(7) . . . . ?
F21B F20A F20B C16 31.0(9) . . . . ?
C16 F20A F20B F19A -3(2) . . . . ?
F21B F20A F20B F19A 28(3) . . . . ?
F21A C16 F20B F20A -84.1(17) . . . . ?
F19B C16 F20B F20A -140.3(13) . . . . ?
F19A C16 F20B F20A -178.0(14) . . . . ?
F21B C16 F20B F20A -37.2(15) . . . . ?
C17 C16 F20B F20A 88.2(13) . . . . ?
F21A C16 F20B F19A 93.9(12) . . . . ?
F20A C16 F20B F19A 178.0(14) . . . . ?
F19B C16 F20B F19A 37.8(8) . . . . ?
F21B C16 F20B F19A 140.9(9) . . . . ?
C17 C16 F20B F19A -93.8(8) . . . . ?
F19B F19A F20B F20A -36(3) . . . . ?
C16 F19A F20B F20A 3(2) . . . . ?
F19B F19A F20B C16 -38.8(6) . . . . ?
F19A F19B F21A F21B -15(2) . . . . ?
C16 F19B F21A F21B -30.7(15) . . . . ?
154

F19A F19B F21A C16 15.8(8) . . . . ?

F20B C16 F21A F21B 76.0(17) . . . . ?
F20A C16 F21A F21B 33.0(12) . . . . ?
F19B C16 F21A F21B 159.3(11) . . . . ?
F19A C16 F21A F21B 145.6(9) . . . . ?
C17 C16 F21A F21B -96.7(9) . . . . ?
F20B C16 F21A F19B -83.2(14) . . . . ?
F20A C16 F21A F19B -126.3(9) . . . . ?
F19A C16 F21A F19B -13.6(8) . . . . ?
F21B C16 F21A F19B -159.3(11) . . . . ?
C17 C16 F21A F19B 104.1(7) . . . . ?
F19B F21A F21B C16 29.5(14) . . . . ?
F19B F21A F21B F20A 4.7(19) . . . . ?
C16 F21A F21B F20A -24.9(7) . . . . ?
F20B C16 F21B F21A -125.7(11) . . . . ?
F20A C16 F21B F21A -148.9(10) . . . . ?
F19B C16 F21B F21A -16.7(10) . . . . ?
F19A C16 F21B F21A -60.2(16) . . . . ?
C17 C16 F21B F21A 103.2(9) . . . . ?
F20B C16 F21B F20A 23.2(10) . . . . ?
F21A C16 F21B F20A 148.9(10) . . . . ?
F19B C16 F21B F20A 132.2(7) . . . . ?
F19A C16 F21B F20A 88.7(13) . . . . ?
C17 C16 F21B F20A -107.9(6) . . . . ?
F20B F20A F21B F21A -7.2(17) . . . . ?
C16 F20A F21B F21A 27.2(8) . . . . ?
F20B F20A F21B C16 -34.5(12) . . . . ?
F23B C20 F22A F22B -147.8(15) . . . . ?
F24A C20 F22A F22B -27.7(18) . . . . ?
F24B C20 F22A F22B -50(2) . . . . ?
F23A C20 F22A F22B -144.1(14) . . . . ?
C19 C20 F22A F22B 100.1(13) . . . . ?
F22B C20 F22A F23B 147.8(15) . . . . ?
F24A C20 F22A F23B 120.2(10) . . . . ?
F24B C20 F22A F23B 97.3(13) . . . . ?
F23A C20 F22A F23B 3.7(10) . . . . ?
C19 C20 F22A F23B -112.1(6) . . . . ?
F23B F22A F22B C20 -23.6(10) . . . . ?
C20 F22A F22B F24A 25.6(14) . . . . ?
F23B F22A F22B F24A 2(2) . . . . ?
F23B C20 F22B F22A 34.5(16) . . . . ?
F24A C20 F22B F22A 153.8(16) . . . . ?
F24B C20 F22B F22A 142.8(15) . . . . ?
F23A C20 F22B F22A 49.5(19) . . . . ?
155

C19 C20 F22B F22A -94.8(14) . . . . ?

F23B C20 F22B F24A -119.3(10) . . . . ?
F24B C20 F22B F24A -11.0(13) . . . . ?
F23A C20 F22B F24A -104.3(14) . . . . ?
F22A C20 F22B F24A -153.8(16) . . . . ?
C19 C20 F22B F24A 111.4(7) . . . . ?
F22B C20 F23A F23B -37(3) . . . . ?
F24A C20 F23A F23B -128(2) . . . . ?
F24B C20 F23A F23B -139(3) . . . . ?
F22A C20 F23A F23B -9(3) . . . . ?
C19 C20 F23A F23B 108(2) . . . . ?
F22B C20 F23A F24B 102.1(14) . . . . ?
F23B C20 F23A F24B 139(3) . . . . ?
F24A C20 F23A F24B 11.5(16) . . . . ?
F22A C20 F23A F24B 130.0(10) . . . . ?
C19 C20 F23A F24B -112.4(10) . . . . ?
F24B F23A F23B C20 -30.6(16) . . . . ?
C20 F23A F23B F22A 11(3) . . . . ?
F24B F23A F23B F22A -20(4) . . . . ?
F22B C20 F23B F23A 151(2) . . . . ?
F24A C20 F23B F23A 61(3) . . . . ?
F24B C20 F23B F23A 41(3) . . . . ?
F22A C20 F23B F23A 171(3) . . . . ?
C19 C20 F23B F23A -80(2) . . . . ?
F22B C20 F23B F22A -20.0(9) . . . . ?
F24A C20 F23B F22A -109.5(13) . . . . ?
F24B C20 F23B F22A -129.5(11) . . . . ?
F23A C20 F23B F22A -171(3) . . . . ?
C19 C20 F23B F22A 108.5(7) . . . . ?
F22B F22A F23B F23A 16(5) . . . . ?
C20 F22A F23B F23A -13(4) . . . . ?
F22B F22A F23B C20 29.2(13) . . . . ?
F22B C20 F24A F24B -156(3) . . . . ?
F23B C20 F24A F24B -47(3) . . . . ?
F23A C20 F24A F24B -26(3) . . . . ?
F22A C20 F24A F24B -140(3) . . . . ?
C19 C20 F24A F24B 95(3) . . . . ?
F23B C20 F24A F22B 108.7(13) . . . . ?
F24B C20 F24A F22B 156(3) . . . . ?
F23A C20 F24A F22B 130.4(10) . . . . ?
F22A C20 F24A F22B 16.4(12) . . . . ?
C19 C20 F24A F22B -109.4(8) . . . . ?
F22A F22B F24A F24B -3(5) . . . . ?
C20 F22B F24A F24B 30(3) . . . . ?
156

F22A F22B F24A C20 -32.7(18) . . . . ?

F22B F24A F24B C20 -23(2) . . . . ?
C20 F24A F24B F23A 20(2) . . . . ?
F22B F24A F24B F23A -2(4) . . . . ?
F22B C20 F24B F24A 24(3) . . . . ?
F23B C20 F24B F24A 140(3) . . . . ?
F23A C20 F24B F24A 156(3) . . . . ?
F22A C20 F24B F24A 52(3) . . . . ?
C19 C20 F24B F24A -98(3) . . . . ?
F22B C20 F24B F23A -131.4(10) . . . . ?
F23B C20 F24B F23A -15.4(12) . . . . ?
F24A C20 F24B F23A -156(3) . . . . ?
F22A C20 F24B F23A -103.2(12) . . . . ?
C19 C20 F24B F23A 106.9(8) . . . . ?
F23B F23A F24B F24A 14(4) . . . . ?
C20 F23A F24B F24A -26(3) . . . . ?
F23B F23A F24B C20 40(2) . . . . ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1N O1 0.97 1.94 2.904(3) 172.4 .
_diffrn_measured_fraction_theta_max 0.989
_diffrn_reflns_theta_full
30.05
_diffrn_measured_fraction_theta_full 0.989
_refine_diff_density_max 1.161
_refine_diff_density_min -0.919
_refine_diff_density_rms 0.134
# END OF CIF

157

Table A-6. CIF File For [Cu3(hfac)6(OH)2](quinuclidinium)2

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
bis(quinuclidinium)
hexakis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)dihydroxotricuprate(II)
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety '2(C7 H14 N 1+), C30 H8 Cu3 F36 O14 2-'
_chemical_formula_sum 'C44 H36 Cu3 F36 N2 O14'
_chemical_formula_weight
1691.37
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_space_group_name_H-M 'P 43 21 2
_symmetry_cell_setting 'Tetragonal'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y+1/2, -z+1/4'
'-x+1/2, y+1/2, -z+3/4'
'-y, -x, -z+1/2'
'y, x, -z'
158

'

'y+1/2, -x+1/2, z+1/4'

'-y+1/2, x+1/2, z+3/4'
_cell_length_a
13.567(2)
_cell_length_b
13.567(2)
_cell_length_c
32.132(5)
_cell_angle_alpha
90
_cell_angle_beta
90
_cell_angle_gamma
90
_cell_volume
5914.3(15)
_cell_formula_units_Z
4
_cell_measurement_temperature 100
_cell_measurement_reflns_used 25
_cell_measurement_theta_min
11.5
_cell_measurement_theta_max
12.4
_exptl_crystal_description
fragment
_exptl_crystal_colour
'blue-green'
_exptl_crystal_size_max
0.65
_exptl_crystal_size_mid
0.52
_exptl_crystal_size_min
0.30
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.900
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
3348
_exptl_absorpt_coefficient_mu 1.246
_exptl_absorpt_correction_type 'psi-scan'
_exptl_absorpt_correction_T_min 0.42
_exptl_absorpt_correction_T_max 0.69
_exptl_absorpt_process_details
;
(North, et al, 1968)
;
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
100
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
159

_diffrn_measurement_device_type 'Enraf-Nonius CAD4 (with Oxford Cryostream)'

_diffrn_measurement_method '\w-2\q scan'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
3
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time 60
_diffrn_standards_decay_% 11.6
_diffrn_reflns_number 9382
_diffrn_reflns_av_R_equivalents 0.198
_diffrn_reflns_av_sigmaI/netI 0.0864
_diffrn_reflns_limit_h_min
0
_diffrn_reflns_limit_h_max 19
_diffrn_reflns_limit_k_min -19
_diffrn_reflns_limit_k_max
0
_diffrn_reflns_limit_l_min
0
_diffrn_reflns_limit_l_max 45
_diffrn_reflns_theta_min
2.2
_diffrn_reflns_theta_max
30.0
_reflns_number_total
8557
_reflns_number_gt
6922
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
'CAD4 EXPRESS (Enraf-Nonius, 1994)'
_computing_cell_refinement
'CAD4 EXPRESS (Enraf-Nonius, 1994)'
_computing_data_reduction
'maXus (Mackay, et al., 1999)'
_computing_structure_solution 'SIR92 (Altomare et al., 1994)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics 'ORTEP-III (Burnett & Johnson, 1996)'
_computing_publication_material 'SHELXL-97 (Sheldrick, 1997)'
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
160

_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1841P)^2^+13.1166P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment constr
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_abs_structure_details
'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack -0.04(2)
_refine_ls_number_reflns
8557
_refine_ls_number_parameters
446
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.115
_refine_ls_R_factor_gt
0.090
_refine_ls_wR_factor_ref
0.2794
_refine_ls_wR_factor_gt
0.2367
_refine_ls_goodness_of_fit_ref 1.108
_refine_ls_restrained_S_all
1.108
_refine_ls_shift/su_max
0.001
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.54334(5) 0.45666(5) 0.7500 0.0174(2) Uani 1 2 d S . .
Cu2 Cu 0.32397(6) 0.43173(6) 0.71883(2) 0.01797(19) Uani 1 1 d . . .
F1 F 0.1091(4) 0.5379(4) 0.78476(19) 0.0389(11) Uani 1 1 d . . .
F2 F 0.0740(3) 0.6871(4) 0.76836(18) 0.0411(12) Uani 1 1 d . . .
F3 F 0.1432(4) 0.6547(4) 0.82707(16) 0.0398(12) Uani 1 1 d . . .
F4 F 0.1707(6) 0.6858(5) 0.6486(2) 0.065(2) Uani 1 1 d . . .
F5 F 0.0459(4) 0.6027(5) 0.62932(19) 0.0516(16) Uani 1 1 d . . .
161

F6 F 0.1851(5) 0.5785(6) 0.60090(18) 0.0577(19) Uani 1 1 d . . .

F7 F -0.0539(5) 0.3581(9) 0.7219(3) 0.094(4) Uani 1 1 d . . .
F8 F 0.0399(5) 0.2972(7) 0.7671(2) 0.076(3) Uani 1 1 d . . .
F9 F 0.0331(12) 0.2400(10) 0.7068(5) 0.151(7) Uani 1 1 d . . .
F10 F 0.3770(6) 0.1759(4) 0.61411(17) 0.0581(19) Uani 1 1 d . . .
F11 F 0.2684(5) 0.1026(6) 0.6525(2) 0.065(2) Uani 1 1 d . . .
F12 F 0.4172(6) 0.0667(4) 0.65900(19) 0.0564(18) Uani 1 1 d . . .
F13 F 0.4122(5) 0.1096(3) 0.80200(15) 0.0373(12) Uani 1 1 d . . .
F14 F 0.3494(4) 0.2372(4) 0.83101(14) 0.0345(10) Uani 1 1 d . . .
F15 F 0.5034(4) 0.2358(4) 0.81535(16) 0.0344(10) Uani 1 1 d . . .
F16 F 0.8535(6) 0.4033(6) 0.8140(3) 0.082(3) Uani 1 1 d . . .
F17 F 0.8228(5) 0.2506(5) 0.8205(3) 0.063(2) Uani 1 1 d . . .
F18 F 0.7419(6) 0.3568(8) 0.8555(2) 0.080(3) Uani 1 1 d . . .
O1 O 0.4473(3) 0.5014(3) 0.70988(14) 0.0187(8) Uani 1 1 d . . .
H1O H 0.4427 0.5649 0.7156 0.022 Uiso 1 1 d . . .
O2 O 0.2992(3) 0.5671(3) 0.77223(14) 0.0214(9) Uani 1 1 d . . .
O3 O 0.2599(4) 0.5208(3) 0.67848(15) 0.0211(9) Uani 1 1 d . . .
O4 O 0.1989(4) 0.3657(4) 0.73083(17) 0.0264(10) Uani 1 1 d . . .
O5 O 0.3573(4) 0.3094(4) 0.67267(15) 0.0255(10) Uani 1 1 d . . .
O6 O 0.3878(4) 0.3470(4) 0.76116(15) 0.0218(9) Uani 1 1 d . . .
O7 O 0.6442(4) 0.4166(4) 0.78979(16) 0.0255(10) Uani 1 1 d . . .
C1 C 0.1407(5) 0.6294(5) 0.7872(2) 0.0260(14) Uani 1 1 d . . .
C2 C 0.2456(5) 0.6408(5) 0.76786(19) 0.0188(11) Uani 1 1 d . . .
C3 C 0.2681 0.7319 0.7500 0.0250(18) Uani 1 2 d S . .
H3 H 0.2186 0.7814 0.7500 0.030 Uiso 1 2 calc SR . .
C4 C 0.1410(5) 0.5965(6) 0.6362(2) 0.0302(15) Uani 1 1 d . . .
C5 C 0.1707(5) 0.5193(5) 0.6693(2) 0.0225(12) Uani 1 1 d . . .
C6 C 0.0966(5) 0.4575(7) 0.6845(2) 0.0309(15) Uani 1 1 d . . .
H6 H 0.0308 0.4646 0.6748 0.037 Uiso 1 1 calc R . .
C7 C 0.1192(5) 0.3850(6) 0.7139(2) 0.0289(15) Uani 1 1 d . . .
C8 C 0.0342(8) 0.3172(10) 0.7279(3) 0.053(3) Uani 1 1 d . . .
C9 C 0.3587(7) 0.1431(6) 0.6518(2) 0.0322(16) Uani 1 1 d . . .
C10 C 0.3649(5) 0.2238(5) 0.6848(2) 0.0232(12) Uani 1 1 d . . .
C11 C 0.3792(6) 0.1902(5) 0.7266(2) 0.0269(14) Uani 1 1 d . . .
H11 H 0.3803 0.1213 0.7318 0.032 Uiso 1 1 calc R . .
C12 C 0.3913(5) 0.2540(5) 0.7598(2) 0.0199(11) Uani 1 1 d . . .
C13 C 0.4146(6) 0.2075(5) 0.8024(2) 0.0261(14) Uani 1 1 d . . .
C14 C 0.7822(6) 0.3388(7) 0.8188(3) 0.040(2) Uani 1 1 d . . .
C15 C 0.7066(5) 0.3474(6) 0.7839(3) 0.0285(15) Uani 1 1 d . . .
C16 C 0.7144 0.2856 0.7500 0.030(2) Uani 1 2 d S . .
H16 H 0.7639 0.2361 0.7500 0.036 Uiso 1 2 calc SR . .
N1 N 0.4745(5) 0.5325(5) 0.62777(17) 0.0239(11) Uani 1 1 d . . .
H1N H 0.4662 0.5134 0.6554 0.029 Uiso 1 1 calc R . .
C17 C 0.4399(7) 0.6360(6) 0.6234(2) 0.0331(16) Uani 1 1 d . . .
162

H17A H 0.4839 0.6808 0.6391 0.040 Uiso 1 1 calc R . .

H17B H 0.3724 0.6426 0.6347 0.040 Uiso 1 1 calc R . .
C18 C 0.4409(7) 0.6634(6) 0.5767(2) 0.0343(16) Uani 1 1 d . . .
H18A H 0.3725 0.6676 0.5661 0.041 Uiso 1 1 calc R . .
H18B H 0.4727 0.7284 0.5729 0.041 Uiso 1 1 calc R . .
C19 C 0.4979(7) 0.5846(6) 0.5526(2) 0.0325(16) Uani 1 1 d . . .
H19 H 0.5070 0.6054 0.5230 0.039 Uiso 1 1 calc R . .
C20 C 0.4158(6) 0.4637(5) 0.6007(2) 0.0265(13) Uani 1 1 d . . .
H20A H 0.3444 0.4723 0.6060 0.032 Uiso 1 1 calc R . .
H20B H 0.4337 0.3945 0.6067 0.032 Uiso 1 1 calc R . .
C21 C 0.4402(7) 0.4893(6) 0.5548(2) 0.0325(16) Uani 1 1 d . . .
H21A H 0.4794 0.4354 0.5423 0.039 Uiso 1 1 calc R . .
H21B H 0.3783 0.4961 0.5387 0.039 Uiso 1 1 calc R . .
C22 C 0.5824(6) 0.5252(8) 0.6172(2) 0.039(2) Uani 1 1 d . . .
H22A H 0.6039 0.4555 0.6177 0.047 Uiso 1 1 calc R . .
H22B H 0.6221 0.5623 0.6378 0.047 Uiso 1 1 calc R . .
C23 C 0.5968(7) 0.5691(8) 0.5733(3) 0.046(2) Uani 1 1 d . . .
H23A H 0.6320 0.6328 0.5754 0.055 Uiso 1 1 calc R . .
H23B H 0.6373 0.5238 0.5563 0.055 Uiso 1 1 calc R . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0162(3) 0.0162(3) 0.0196(5) -0.0012(3) -0.0012(3) 0.0020(4)
Cu2 0.0171(3) 0.0172(4) 0.0196(3) 0.0017(3) -0.0012(3) -0.0010(3)
F1 0.026(2) 0.031(2) 0.060(3) -0.012(2) 0.009(2) -0.0083(18)
F2 0.019(2) 0.048(3) 0.057(3) 0.002(2) 0.005(2) 0.0060(19)
F3 0.033(2) 0.055(3) 0.032(2) -0.013(2) 0.0123(19) -0.008(2)
F4 0.093(5) 0.028(3) 0.074(4) 0.013(3) -0.037(4) 0.005(3)
F5 0.024(2) 0.080(5) 0.051(3) 0.026(3) -0.010(2) 0.008(3)
F6 0.052(4) 0.087(5) 0.034(3) 0.024(3) 0.009(2) 0.031(3)
F7 0.030(3) 0.161(9) 0.090(6) 0.063(6) -0.012(4) -0.030(4)
F8 0.044(3) 0.126(7) 0.056(4) 0.050(4) -0.005(3) -0.036(4)
F9 0.194(14) 0.104(8) 0.155(11) -0.039(8) 0.052(11) -0.120(10)
F10 0.122(6) 0.029(3) 0.023(2) -0.004(2) 0.012(3) 0.005(3)
F11 0.051(4) 0.066(4) 0.077(5) -0.038(4) 0.001(3) -0.023(3)
F12 0.097(5) 0.025(2) 0.047(3) -0.015(2) -0.018(3) 0.019(3)
F13 0.062(3) 0.018(2) 0.031(2) 0.0071(17) -0.007(2) -0.002(2)
F14 0.043(3) 0.038(3) 0.0224(19) 0.0057(18) 0.0040(19) -0.003(2)
163

F15 0.029(2) 0.036(3) 0.038(2) 0.008(2) -0.0128(19) -0.0022(19)

F16 0.048(4) 0.075(5) 0.122(7) 0.048(5) -0.052(4) -0.025(4)
F17 0.046(3) 0.048(4) 0.095(5) 0.032(4) -0.021(4) 0.015(3)
F18 0.061(5) 0.126(8) 0.053(4) 0.007(4) -0.022(4) 0.040(5)
O1 0.018(2) 0.0166(19) 0.021(2) -0.0010(15) -0.0026(16) -0.0020(15)
O2 0.022(2) 0.020(2) 0.022(2) 0.0019(17) -0.0011(16) 0.0027(17)
O3 0.020(2) 0.021(2) 0.022(2) 0.0037(17) -0.0022(17) 0.0027(16)
O4 0.022(2) 0.027(2) 0.030(2) 0.000(2) -0.0013(19) -0.0066(19)
O5 0.032(3) 0.023(2) 0.021(2) -0.0009(18) -0.0031(19) 0.0008(19)
O6 0.024(2) 0.021(2) 0.021(2) 0.0031(16) -0.0019(17) 0.0009(17)
O7 0.021(2) 0.023(2) 0.032(3) 0.0057(19) -0.0030(19) 0.0033(17)
C1 0.019(3) 0.028(3) 0.031(3) -0.007(3) 0.010(3) 0.004(2)
C2 0.016(3) 0.025(3) 0.015(2) -0.005(2) 0.000(2) 0.004(2)
C3 0.022(3) 0.022(3) 0.030(5) -0.003(3) -0.003(3) 0.007(3)
C4 0.020(3) 0.039(4) 0.031(3) 0.010(3) -0.007(3) 0.007(3)
C5 0.022(3) 0.026(3) 0.019(3) 0.003(2) -0.008(2) 0.000(2)
C6 0.021(3) 0.050(5) 0.022(3) 0.001(3) 0.003(2) -0.005(3)
C7 0.021(3) 0.042(4) 0.024(3) -0.001(3) -0.002(3) -0.013(3)
C8 0.039(5) 0.077(8) 0.043(5) 0.017(5) -0.005(4) -0.031(5)
C9 0.052(5) 0.022(3) 0.023(3) -0.003(3) 0.003(3) 0.002(3)
C10 0.026(3) 0.018(3) 0.026(3) -0.003(2) 0.000(2) -0.001(2)
C11 0.041(4) 0.013(3) 0.027(3) 0.002(2) -0.003(3) -0.002(2)
C12 0.022(3) 0.018(3) 0.019(3) 0.002(2) 0.000(2) -0.001(2)
C13 0.036(4) 0.019(3) 0.023(3) 0.003(2) -0.002(3) -0.002(3)
C14 0.021(3) 0.043(5) 0.055(5) 0.018(4) -0.013(3) 0.004(3)
C15 0.016(3) 0.030(3) 0.040(4) 0.018(3) 0.000(3) 0.002(2)
C16 0.021(3) 0.021(3) 0.047(6) 0.003(3) 0.003(3) 0.007(3)
N1 0.026(3) 0.030(3) 0.016(2) -0.001(2) -0.004(2) 0.001(2)
C17 0.041(4) 0.031(4) 0.028(3) -0.007(3) 0.012(3) -0.011(3)
C18 0.050(5) 0.022(3) 0.032(3) 0.001(3) 0.005(3) 0.003(3)
C19 0.051(5) 0.030(4) 0.017(3) 0.003(3) 0.007(3) 0.004(3)
C20 0.032(3) 0.021(3) 0.026(3) -0.003(2) 0.004(3) -0.004(3)
C21 0.053(5) 0.024(3) 0.020(3) 0.000(2) -0.009(3) 0.001(3)
C22 0.017(3) 0.071(6) 0.030(4) 0.011(4) -0.001(3) 0.003(3)
C23 0.036(4) 0.055(6) 0.047(5) 0.008(4) 0.015(4) 0.001(4)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
164

;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O1 1.931(5) . ?
Cu1 O1 1.931(5) 5_666 ?
Cu1 O7 1.949(5) 5_666 ?
Cu1 O7 1.949(5) . ?
Cu2 O1 1.943(5) . ?
Cu2 O4 1.958(5) . ?
Cu2 O3 1.974(5) . ?
Cu2 O6 1.980(5) . ?
Cu2 O5 2.271(5) . ?
F1 C1 1.316(9) . ?
F2 C1 1.340(9) . ?
F3 C1 1.327(9) . ?
F4 C4 1.337(11) . ?
F5 C4 1.312(9) . ?
F6 C4 1.307(10) . ?
F7 C8 1.332(15) . ?
F8 C8 1.292(11) . ?
F9 C8 1.247(18) . ?
F10 C9 1.315(9) . ?
F11 C9 1.342(11) . ?
F12 C9 1.325(10) . ?
F13 C13 1.328(8) . ?
F14 C13 1.339(9) . ?
F15 C13 1.332(9) . ?
F16 C14 1.314(12) . ?
F17 C14 1.320(11) . ?
F18 C14 1.321(13) . ?
O1 H1O 0.88 . ?
O2 C2 1.244(8) . ?
O3 C5 1.246(8) . ?
O4 C7 1.237(9) . ?
O5 C10 1.229(8) . ?
O6 C12 1.263(8) . ?
O7 C15 1.279(9) . ?
C1 C2 1.561(9) . ?
C2 C3 1.396(7) . ?
165

C3 C2 1.396(7) 5_666 ?
C3 H3 0.9500 . ?
C4 C5 1.545(10) . ?
C5 C6 1.398(10) . ?
C6 C7 1.400(12) . ?
C6 H6 0.9500 . ?
C7 C8 1.541(11) . ?
C9 C10 1.526(10) . ?
C10 C11 1.433(10) . ?
C11 C12 1.382(9) . ?
C11 H11 0.9500 . ?
C12 C13 1.540(9) . ?
C14 C15 1.523(11) . ?
C15 C16 1.379(9) . ?
C16 C15 1.379(9) 5_666 ?
C16 H16 0.9500 . ?
N1 C17 1.488(11) . ?
N1 C20 1.503(9) . ?
N1 C22 1.506(10) . ?
N1 H1N 0.9300 . ?
C17 C18 1.545(11) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
C18 C19 1.529(11) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 C23 1.513(14) . ?
C19 C21 1.513(12) . ?
C19 H19 1.0000 . ?
C20 C21 1.552(10) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 C23 1.544(12) . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
166

_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Cu1 O1 91.2(3) . 5_666 ?
O1 Cu1 O7 88.3(2) . 5_666 ?
O1 Cu1 O7 177.4(2) 5_666 5_666 ?
O1 Cu1 O7 177.4(2) . . ?
O1 Cu1 O7 88.3(2) 5_666 . ?
O7 Cu1 O7 92.2(3) 5_666 . ?
O1 Cu2 O4 176.7(2) . . ?
O1 Cu2 O3 89.1(2) . . ?
O4 Cu2 O3 91.6(2) . . ?
O1 Cu2 O6 90.4(2) . . ?
O4 Cu2 O6 88.7(2) . . ?
O3 Cu2 O6 177.5(2) . . ?
O1 Cu2 O5 95.00(19) . . ?
O4 Cu2 O5 88.1(2) . . ?
O3 Cu2 O5 96.09(19) . . ?
O6 Cu2 O5 86.40(19) . . ?
Cu1 O1 Cu2 109.2(2) . . ?
Cu1 O1 H1O 102.5 . . ?
Cu2 O1 H1O 112.5 . . ?
C5 O3 Cu2 125.0(4) . . ?
C7 O4 Cu2 125.0(5) . . ?
C10 O5 Cu2 120.0(5) . . ?
C12 O6 Cu2 124.9(4) . . ?
C15 O7 Cu1 125.0(5) . . ?
F1 C1 F3 108.0(7) . . ?
F1 C1 F2 107.8(6) . . ?
F3 C1 F2 107.6(6) . . ?
F1 C1 C2 111.5(5) . . ?
F3 C1 C2 109.5(6) . . ?
F2 C1 C2 112.2(6) . . ?
O2 C2 C3 129.0(6) . . ?
O2 C2 C1 114.1(6) . . ?
C3 C2 C1 116.8(5) . . ?
C2 C3 C2 123.8(5) 5_666 . ?
C2 C3 H3 118.1 5_666 . ?
C2 C3 H3 118.1 . . ?
F6 C4 F5 108.3(7) . . ?
F6 C4 F4 106.9(8) . . ?
F5 C4 F4 106.8(7) . . ?
F6 C4 C5 110.5(6) . . ?
167

F5 C4 C5 114.6(7) . . ?
F4 C4 C5 109.4(6) . . ?
O3 C5 C6 128.7(7) . . ?
O3 C5 C4 113.9(6) . . ?
C6 C5 C4 117.3(6) . . ?
C5 C6 C7 120.0(7) . . ?
C5 C6 H6 120.0 . . ?
C7 C6 H6 120.0 . . ?
O4 C7 C6 129.6(7) . . ?
O4 C7 C8 113.6(8) . . ?
C6 C7 C8 116.8(7) . . ?
F9 C8 F8 110.9(13) . . ?
F9 C8 F7 105.1(12) . . ?
F8 C8 F7 106.3(10) . . ?
F9 C8 C7 110.6(10) . . ?
F8 C8 C7 111.3(8) . . ?
F7 C8 C7 112.4(10) . . ?
F10 C9 F12 108.2(7) . . ?
F10 C9 F11 109.1(8) . . ?
F12 C9 F11 102.9(7) . . ?
F10 C9 C10 112.7(6) . . ?
F12 C9 C10 114.0(7) . . ?
F11 C9 C10 109.5(7) . . ?
O5 C10 C11 127.5(6) . . ?
O5 C10 C9 117.0(6) . . ?
C11 C10 C9 115.5(6) . . ?
C12 C11 C10 122.7(6) . . ?
C12 C11 H11 118.7 . . ?
C10 C11 H11 118.7 . . ?
O6 C12 C11 130.4(6) . . ?
O6 C12 C13 112.7(6) . . ?
C11 C12 C13 116.9(6) . . ?
F13 C13 F15 108.2(6) . . ?
F13 C13 F14 107.0(6) . . ?
F15 C13 F14 107.2(6) . . ?
F13 C13 C12 113.4(6) . . ?
F15 C13 C12 110.2(6) . . ?
F14 C13 C12 110.6(6) . . ?
F16 C14 F17 107.5(8) . . ?
F16 C14 F18 106.6(11) . . ?
F17 C14 F18 107.7(8) . . ?
F16 C14 C15 111.1(7) . . ?
F17 C14 C15 112.4(9) . . ?
F18 C14 C15 111.4(7) . . ?
168

O7 C15 C16 127.8(6) . . ?

O7 C15 C14 113.2(8) . . ?
C16 C15 C14 118.9(6) . . ?
C15 C16 C15 122.2(6) 5_666 . ?
C15 C16 H16 118.9 5_666 . ?
C15 C16 H16 118.9 . . ?
C17 N1 C20 111.3(6) . . ?
C17 N1 C22 110.3(7) . . ?
C20 N1 C22 110.1(6) . . ?
C17 N1 H1N 108.3 . . ?
C20 N1 H1N 108.3 . . ?
C22 N1 H1N 108.3 . . ?
N1 C17 C18 108.4(6) . . ?
N1 C17 H17A 110.0 . . ?
C18 C17 H17A 110.0 . . ?
N1 C17 H17B 110.0 . . ?
C18 C17 H17B 110.0 . . ?
H17A C17 H17B 108.4 . . ?
C19 C18 C17 109.1(7) . . ?
C19 C18 H18A 109.9 . . ?
C17 C18 H18A 109.9 . . ?
C19 C18 H18B 109.9 . . ?
C17 C18 H18B 109.9 . . ?
H18A C18 H18B 108.3 . . ?
C23 C19 C21 108.6(7) . . ?
C23 C19 C18 108.9(7) . . ?
C21 C19 C18 108.2(7) . . ?
C23 C19 H19 110.4 . . ?
C21 C19 H19 110.4 . . ?
C18 C19 H19 110.4 . . ?
N1 C20 C21 107.3(6) . . ?
N1 C20 H20A 110.2 . . ?
C21 C20 H20A 110.2 . . ?
N1 C20 H20B 110.2 . . ?
C21 C20 H20B 110.2 . . ?
H20A C20 H20B 108.5 . . ?
C19 C21 C20 110.2(6) . . ?
C19 C21 H21A 109.6 . . ?
C20 C21 H21A 109.6 . . ?
C19 C21 H21B 109.6 . . ?
C20 C21 H21B 109.6 . . ?
H21A C21 H21B 108.1 . . ?
N1 C22 C23 107.7(6) . . ?
N1 C22 H22A 110.2 . . ?
169

C23 C22 H22A 110.2 . . ?

N1 C22 H22B 110.2 . . ?
C23 C22 H22B 110.2 . . ?
H22A C22 H22B 108.5 . . ?
C19 C23 C22 110.0(7) . . ?
C19 C23 H23A 109.7 . . ?
C22 C23 H23A 109.7 . . ?
C19 C23 H23B 109.7 . . ?
C22 C23 H23B 109.7 . . ?
H23A C23 H23B 108.2 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 Cu1 O1 Cu2 -87.1(2) 5_666 . . . ?
O7 Cu1 O1 Cu2 90.3(2) 5_666 . . . ?
O7 Cu1 O1 Cu2 -167(5) . . . . ?
O4 Cu2 O1 Cu1 69(4) . . . . ?
O3 Cu2 O1 Cu1 171.3(2) . . . . ?
O6 Cu2 O1 Cu1 -6.2(2) . . . . ?
O5 Cu2 O1 Cu1 -92.6(2) . . . . ?
O1 Cu2 O3 C5 -177.4(6) . . . . ?
O4 Cu2 O3 C5 -0.6(6) . . . . ?
O6 Cu2 O3 C5 -98(5) . . . . ?
O5 Cu2 O3 C5 87.6(6) . . . . ?
O1 Cu2 O4 C7 104(4) . . . . ?
O3 Cu2 O4 C7 1.8(7) . . . . ?
O6 Cu2 O4 C7 179.3(7) . . . . ?
O5 Cu2 O4 C7 -94.3(6) . . . . ?
O1 Cu2 O5 C10 116.9(6) . . . . ?
O4 Cu2 O5 C10 -62.0(6) . . . . ?
O3 Cu2 O5 C10 -153.4(6) . . . . ?
O6 Cu2 O5 C10 26.8(6) . . . . ?
O1 Cu2 O6 C12 -122.7(5) . . . . ?
O4 Cu2 O6 C12 60.5(5) . . . . ?
O3 Cu2 O6 C12 158(5) . . . . ?
170

O5 Cu2 O6 C12 -27.7(5) . . . . ?

O1 Cu1 O7 C15 -101(5) . . . . ?
O1 Cu1 O7 C15 178.5(6) 5_666 . . . ?
O7 Cu1 O7 C15 1.1(5) 5_666 . . . ?
F1 C1 C2 O2 -33.1(9) . . . . ?
F3 C1 C2 O2 86.5(7) . . . . ?
F2 C1 C2 O2 -154.1(6) . . . . ?
F1 C1 C2 C3 149.7(6) . . . . ?
F3 C1 C2 C3 -90.8(7) . . . . ?
F2 C1 C2 C3 28.6(8) . . . . ?
O2 C2 C3 C2 2.0(5) . . . 5_666 ?
C1 C2 C3 C2 178.8(6) . . . 5_666 ?
Cu2 O3 C5 C6 0.1(11) . . . . ?
Cu2 O3 C5 C4 -179.2(5) . . . . ?
F6 C4 C5 O3 63.8(9) . . . . ?
F5 C4 C5 O3 -173.4(7) . . . . ?
F4 C4 C5 O3 -53.6(9) . . . . ?
F6 C4 C5 C6 -115.6(8) . . . . ?
F5 C4 C5 C6 7.2(11) . . . . ?
F4 C4 C5 C6 127.0(8) . . . . ?
O3 C5 C6 C7 -0.3(13) . . . . ?
C4 C5 C6 C7 179.0(7) . . . . ?
Cu2 O4 C7 C6 -2.6(13) . . . . ?
Cu2 O4 C7 C8 176.9(6) . . . . ?
C5 C6 C7 O4 1.7(14) . . . . ?
C5 C6 C7 C8 -177.7(8) . . . . ?
O4 C7 C8 F9 -85.4(14) . . . . ?
C6 C7 C8 F9 94.1(15) . . . . ?
O4 C7 C8 F8 38.3(14) . . . . ?
C6 C7 C8 F8 -142.1(11) . . . . ?
O4 C7 C8 F7 157.4(9) . . . . ?
C6 C7 C8 F7 -23.0(14) . . . . ?
Cu2 O5 C10 C11 -16.6(11) . . . . ?
Cu2 O5 C10 C9 163.4(5) . . . . ?
F10 C9 C10 O5 20.3(11) . . . . ?
F12 C9 C10 O5 144.1(8) . . . . ?
F11 C9 C10 O5 -101.3(8) . . . . ?
F10 C9 C10 C11 -159.7(8) . . . . ?
F12 C9 C10 C11 -35.9(11) . . . . ?
F11 C9 C10 C11 78.8(9) . . . . ?
O5 C10 C11 C12 -3.3(13) . . . . ?
C9 C10 C11 C12 176.7(7) . . . . ?
Cu2 O6 C12 C11 19.5(11) . . . . ?
Cu2 O6 C12 C13 -161.4(5) . . . . ?
171

C10 C11 C12 O6 4.0(13) . . . . ?

C10 C11 C12 C13 -175.1(7) . . . . ?
O6 C12 C13 F13 175.9(6) . . . . ?
C11 C12 C13 F13 -4.9(10) . . . . ?
O6 C12 C13 F15 -62.6(8) . . . . ?
C11 C12 C13 F15 116.5(7) . . . . ?
O6 C12 C13 F14 55.7(8) . . . . ?
C11 C12 C13 F14 -125.1(7) . . . . ?
Cu1 O7 C15 C16 -2.3(10) . . . . ?
Cu1 O7 C15 C14 174.9(5) . . . . ?
F16 C14 C15 O7 -81.6(10) . . . . ?
F17 C14 C15 O7 157.9(7) . . . . ?
F18 C14 C15 O7 37.0(11) . . . . ?
F16 C14 C15 C16 95.8(10) . . . . ?
F17 C14 C15 C16 -24.7(10) . . . . ?
F18 C14 C15 C16 -145.6(8) . . . . ?
O7 C15 C16 C15 1.3(6) . . . 5_666 ?
C14 C15 C16 C15 -175.8(7) . . . 5_666 ?
C20 N1 C17 C18 -53.7(8) . . . . ?
C22 N1 C17 C18 68.8(8) . . . . ?
N1 C17 C18 C19 -12.6(10) . . . . ?
C17 C18 C19 C23 -51.3(9) . . . . ?
C17 C18 C19 C21 66.5(9) . . . . ?
C17 N1 C20 C21 67.3(7) . . . . ?
C22 N1 C20 C21 -55.3(8) . . . . ?
C23 C19 C21 C20 65.4(9) . . . . ?
C18 C19 C21 C20 -52.6(9) . . . . ?
N1 C20 C21 C19 -10.6(9) . . . . ?
C17 N1 C22 C23 -54.7(9) . . . . ?
C20 N1 C22 C23 68.6(9) . . . . ?
C21 C19 C23 C22 -52.1(10) . . . . ?
C18 C19 C23 C22 65.5(10) . . . . ?
N1 C22 C23 C19 -11.5(11) . . . . ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1N O1 0.93 1.78 2.697(7) 169.1 .
172

O1 H1O O2 0.88 1.89 2.773(6) 179.9 5_666

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full
30.03
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max 1.621
_refine_diff_density_min -1.862
_refine_diff_density_rms 0.233
# END OF CIF

173

Table A-7. CIF File For [Cu3(hfac)6(HO)2](Et2NH2)2

_audit_creation_method
_chemical_name_systematic

SHELXL-97

bis(diethylammonium)
hexakis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)dihydroxotricuprate(II)
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety '2(C4 H12 N 1+), C30 H8 Cu3 F36 O14 1-'
_chemical_formula_sum
'C38 H32 Cu3 F36 N2 O14'
_chemical_formula_weight
1615.28
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
Monoclinic
_symmetry_space_group_name_H-M C2/c
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
174

'-x+1/2, -y+1/2, -z'

'x+1/2, -y+1/2, z-1/2'
_cell_length_a
16.434(5)
_cell_length_b
20.869(6)
_cell_length_c
16.594(5)
_cell_angle_alpha
90
_cell_angle_beta
99.758(2)
_cell_angle_gamma
90
_cell_volume
5609(3)
_cell_formula_units_Z
4
_cell_measurement_temperature 100
_cell_measurement_reflns_used 16072
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
27.5
_exptl_crystal_description
fragment
_exptl_crystal_colour
'blue-green'
_exptl_crystal_size_max
0.17
_exptl_crystal_size_mid
0.13
_exptl_crystal_size_min
0.08
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.913
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
3188
_exptl_absorpt_coefficient_mu 1.308
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.808
_exptl_absorpt_correction_T_max 0.903
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
100
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
175

_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
_diffrn_reflns_number
16297
_diffrn_reflns_av_R_equivalents 0.022
_diffrn_reflns_av_sigmaI/netI 0.0806
_diffrn_reflns_limit_h_min -21
_diffrn_reflns_limit_h_max 21
_diffrn_reflns_limit_k_min -25
_diffrn_reflns_limit_k_max 27
_diffrn_reflns_limit_l_min -21
_diffrn_reflns_limit_l_max 21
_diffrn_reflns_theta_min
2.7
_diffrn_reflns_theta_max
27.5
_reflns_number_total
6417
_reflns_number_gt
3795
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution ?
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0759P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
176

_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment mixed
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
6417
_refine_ls_number_parameters
438
_refine_ls_number_restraints
1
_refine_ls_R_factor_all
0.090
_refine_ls_R_factor_gt
0.046
_refine_ls_wR_factor_ref
0.129
_refine_ls_wR_factor_gt
0.117
_refine_ls_goodness_of_fit_ref 0.961
_refine_ls_restrained_S_all
0.961
_refine_ls_shift/su_max
0.007
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.01704(3) 0.226093(19) 0.60447(3) 0.03130(14) Uani 1 1 d . . .
Cu2 Cu 0.0000 0.32003(3) 0.7500 0.02933(16) Uani 1 2 d S . .
O1 O 0.09848(15) 0.15663(11) 0.61694(14) 0.0363(6) Uani 1 1 d . . .
O2 O -0.03759(14) 0.19334(11) 0.49863(14) 0.0347(6) Uani 1 1 d . . .
O3 O -0.06727(14) 0.29385(11) 0.60249(14) 0.0320(5) Uani 1 1 d . . .
O5 O -0.06891(14) 0.15641(11) 0.68066(14) 0.0326(6) Uani 1 1 d . . .
O4 O 0.08038(15) 0.29220(13) 0.52467(16) 0.0415(6) Uani 1 1 d . . .
O7 O 0.06892(14) 0.25648(11) 0.71129(14) 0.0286(5) Uani 1 1 d D . .
O6 O 0.06809(16) 0.38488(12) 0.71009(15) 0.0390(6) Uani 1 1 d . . .
F2 F -0.13987(13) 0.13368(11) 0.37048(14) 0.0518(6) Uani 1 1 d . . .
F3 F -0.20051(13) 0.07148(10) 0.65241(15) 0.0497(6) Uani 1 1 d . . .
F15 F -0.11710(14) -0.00675(10) 0.65531(16) 0.0551(7) Uani 1 1 d . . .
F8 F -0.17751(16) 0.42505(12) 0.50967(16) 0.0646(7) Uani 1 1 d . . .
F6 F 0.21671(18) 0.07612(14) 0.65939(16) 0.0821(10) Uani 1 1 d . . .
177

F14 F -0.03200(15) 0.09118(14) 0.33457(15) 0.0703(8) Uani 1 1 d . . .

F13 F -0.12266(19) 0.06538(13) 0.56251(15) 0.0748(9) Uani 1 1 d . . .
F1 F -0.04541(16) 0.19331(14) 0.33217(15) 0.0673(7) Uani 1 1 d . . .
F5 F 0.20882(16) 0.04742(14) 0.53578(16) 0.0723(8) Uani 1 1 d . . .
F18 F 0.1218(2) 0.47218(14) 0.60344(17) 0.0880(10) Uani 1 1 d . . .
F7 F -0.22810(15) 0.33259(12) 0.52758(17) 0.0645(7) Uani 1 1 d . . .
F9 F -0.17331(15) 0.38611(13) 0.63075(14) 0.0641(7) Uani 1 1 d . . .
F17 F 0.1215(2) 0.54522(13) 0.6930(2) 0.0970(11) Uani 1 1 d . . .
F16 F 0.20210(19) 0.46445(14) 0.7194(2) 0.0857(10) Uani 1 1 d . . .
F4 F 0.13104(19) 0.00460(14) 0.6070(2) 0.0923(10) Uani 1 1 d . . .
F10 F 0.0405(3) 0.3469(2) 0.34294(19) 0.1281(16) Uani 1 1 d . . .
F12 F 0.1582(2) 0.34350(19) 0.4185(3) 0.1231(15) Uani 1 1 d . . .
F11 F 0.08311(19) 0.42617(14) 0.41558(18) 0.0795(9) Uani 1 1 d . . .
N1C N 0.23216(19) 0.28384(15) 0.7329(2) 0.0471(8) Uani 1 1 d . B .
H1C1 H 0.2500 0.3160 0.7696 0.057 Uiso 1 1 calc R . .
H1C2 H 0.1763 0.2792 0.7314 0.057 Uiso 1 1 calc R . .
C8 C 0.0000 0.0661(2) 0.7500 0.0314(11) Uani 1 2 d S . .
H8 H 0.0000 0.0206 0.7500 0.020(11) Uiso 1 2 calc SR . .
C7 C -0.0602(2) 0.09748(16) 0.6942(2) 0.0307(8) Uani 1 1 d . . .
C5 C -0.0359(3) 0.3610(2) 0.4952(3) 0.0436(10) Uani 1 1 d . . .
C13 C -0.1650(2) 0.37182(19) 0.5543(2) 0.0440(10) Uani 1 1 d . . .
C1 C 0.0998(2) 0.11151(17) 0.5674(2) 0.0347(8) Uani 1 1 d . . .
C3 C -0.0132(2) 0.14604(18) 0.4632(2) 0.0359(8) Uani 1 1 d . . .
C11 C -0.0577(2) 0.1401(2) 0.3730(3) 0.0499(11) Uani 1 1 d . . .
C15 C -0.1253(2) 0.05642(17) 0.6409(2) 0.0359(9) Uani 1 1 d . . .
C4 C -0.0823(2) 0.33941(16) 0.5506(2) 0.0339(8) Uani 1 1 d . . .
C9 C 0.0604(3) 0.44440(19) 0.7163(2) 0.0487(11) Uani 1 1 d . . .
C6 C 0.0415(3) 0.33503(19) 0.4856(2) 0.0439(10) Uani 1 1 d . . .
C12 C 0.1667(3) 0.0614(2) 0.5940(3) 0.0487(10) Uani 1 1 d . . .
C1C C 0.2733(3) 0.2233(2) 0.7641(3) 0.0695(15) Uani 1 1 d . . .
H1C1 H 0.2458 0.1868 0.7324 0.083 Uiso 1 1 calc R A 1
H1C2 H 0.3316 0.2243 0.7559 0.083 Uiso 1 1 calc R A 1
C2 C 0.0496(2) 0.1033(2) 0.4928(2) 0.0449(10) Uani 1 1 d . . .
H2 H 0.0581 0.0671 0.4605 0.060(13) Uiso 1 1 calc R . .
C14 C 0.0809(3) 0.3634(3) 0.4145(3) 0.0673(14) Uani 1 1 d . . .
C16 C 0.1266(3) 0.4825(2) 0.6821(3) 0.0672(14) Uani 1 1 d . . .
C2C C 0.2708(3) 0.2136(2) 0.8484(3) 0.0543(18) Uani 0.883(12) 1 d P B 1
C2C C 0.3354(19) 0.2002(14) 0.8320(17) 0.028(10) Uiso 0.117(12) 1 d P B 2
C3C C 0.2463(3) 0.3052(3) 0.6488(3) 0.0756(15) Uani 1 1 d . . .
H3C1 H 0.2393 0.2677 0.6117 0.091 Uiso 1 1 calc R B .
H3C2 H 0.2033 0.3369 0.6271 0.091 Uiso 1 1 calc R . .
C10 C 0.0000 0.4772(3) 0.7500 0.0597(18) Uani 1 2 d S . .
H10 H 0.0000 0.5227 0.7500 0.059(18) Uiso 1 2 calc SR . .
C4C C 0.3271(4) 0.3335(3) 0.6469(4) 0.109(2) Uani 1 1 d . B .
178

H4C1 H 0.3348 0.3710 0.6830 0.163 Uiso 1 1 calc R . .

H4C2 H 0.3305 0.3467 0.5909 0.163 Uiso 1 1 calc R . .
H4C3 H 0.3703 0.3019 0.6655 0.163 Uiso 1 1 calc R . .
H5 H -0.055(3) 0.386(2) 0.469(3) 0.063(16) Uiso 1 1 d . . .
H1O H 0.069(3) 0.2244(14) 0.741(2) 0.052(13) Uiso 1 1 d D . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0341(2) 0.0283(2) 0.0297(2) -0.00183(18) 0.00051(18) 0.00475(18)
Cu2 0.0354(3) 0.0234(3) 0.0277(3) 0.000 0.0011(3) 0.000
O1 0.0395(14) 0.0333(14) 0.0343(14) -0.0039(11) 0.0009(11) 0.0073(11)
O2 0.0350(14) 0.0360(14) 0.0314(13) -0.0048(11) 0.0012(11) 0.0044(11)
O3 0.0358(14) 0.0300(13) 0.0286(13) 0.0031(10) 0.0010(10) 0.0065(10)
O5 0.0334(13) 0.0262(13) 0.0365(14) -0.0035(10) 0.0016(11) 0.0001(10)
O4 0.0402(15) 0.0429(16) 0.0404(15) 0.0060(13) 0.0044(12) -0.0004(12)
O7 0.0311(13) 0.0250(13) 0.0288(13) 0.0008(10) 0.0026(10) -0.0012(10)
O6 0.0516(16) 0.0296(15) 0.0330(14) 0.0001(11) -0.0006(12) -0.0099(11)
F2 0.0383(13) 0.0592(15) 0.0525(14) -0.0167(12) -0.0075(10) 0.0084(11)
F3 0.0343(12) 0.0410(13) 0.0710(16) -0.0093(12) 0.0012(11) -0.0044(10)
F15 0.0501(14) 0.0276(12) 0.0820(19) -0.0139(11) -0.0047(13) -0.0055(10)
F8 0.0653(16) 0.0511(15) 0.0750(18) 0.0262(13) 0.0044(13) 0.0254(12)
F6 0.095(2) 0.082(2) 0.0558(17) -0.0267(15) -0.0251(15) 0.0579(17)
F14 0.0633(16) 0.093(2) 0.0485(15) -0.0394(14) -0.0071(12) 0.0333(15)
F13 0.110(2) 0.0777(19) 0.0388(15) -0.0181(13) 0.0172(14) -0.0516(17)
F1 0.0684(18) 0.094(2) 0.0384(14) 0.0112(14) 0.0050(12) 0.0059(15)
F5 0.0622(17) 0.095(2) 0.0585(16) -0.0216(15) 0.0061(13) 0.0412(15)
F18 0.125(3) 0.085(2) 0.0509(18) 0.0157(15) 0.0050(17) -0.0529(19)
F7 0.0448(15) 0.0648(17) 0.0810(19) -0.0094(14) 0.0021(13) 0.0060(12)
F9 0.0654(16) 0.0806(18) 0.0414(14) -0.0115(13) -0.0048(12) 0.0368(14)
F17 0.143(3) 0.0385(17) 0.103(3) 0.0153(15) 0.003(2) -0.0370(17)
F16 0.081(2) 0.076(2) 0.093(2) 0.0286(17) -0.0046(18) -0.0380(16)
F4 0.085(2) 0.0536(18) 0.138(3) 0.0280(18) 0.016(2) 0.0186(15)
F10 0.205(5) 0.143(3) 0.0431(19) -0.004(2) 0.042(2) -0.065(3)
F12 0.115(3) 0.135(3) 0.143(3) 0.073(3) 0.089(3) 0.052(2)
F11 0.097(2) 0.067(2) 0.083(2) 0.0252(16) 0.0406(18) -0.0055(16)
N1C 0.0335(18) 0.041(2) 0.063(2) 0.0005(17) -0.0026(16) -0.0048(14)
C8 0.034(3) 0.018(2) 0.042(3) 0.000 0.006(2) 0.000
C7 0.0271(18) 0.0284(19) 0.038(2) -0.0052(15) 0.0090(15) -0.0015(14)
179

C5 0.057(3) 0.039(2) 0.032(2) 0.0090(19) -0.001(2) 0.008(2)

C13 0.050(2) 0.042(2) 0.036(2) -0.0032(18) -0.0062(19) 0.0062(19)
C1 0.0336(19) 0.034(2) 0.039(2) 0.0004(17) 0.0116(17) 0.0056(15)
C3 0.033(2) 0.041(2) 0.034(2) -0.0090(17) 0.0066(16) 0.0008(16)
C11 0.039(2) 0.055(3) 0.052(3) -0.013(2) -0.003(2) 0.012(2)
C15 0.038(2) 0.031(2) 0.039(2) -0.0032(16) 0.0067(17) -0.0019(15)
C4 0.039(2) 0.0293(19) 0.0301(19) -0.0030(16) -0.0048(16) 0.0033(15)
C9 0.070(3) 0.036(3) 0.033(2) 0.0023(17) -0.011(2) -0.012(2)
C6 0.052(3) 0.041(2) 0.038(2) 0.0058(18) 0.0084(19) -0.0025(19)
C12 0.050(3) 0.049(3) 0.045(3) -0.008(2) 0.004(2) 0.012(2)
C1C 0.054(3) 0.047(3) 0.094(4) -0.010(3) -0.023(3) 0.007(2)
C2 0.044(2) 0.049(2) 0.039(2) -0.0167(19) 0.0008(18) 0.0120(18)
C14 0.069(3) 0.075(4) 0.063(3) 0.019(3) 0.026(3) 0.010(3)
C16 0.091(4) 0.045(3) 0.059(3) 0.012(2) -0.005(3) -0.027(3)
C2C 0.064(4) 0.047(3) 0.051(3) 0.012(2) 0.006(3) -0.005(2)
C3C 0.058(3) 0.115(4) 0.058(3) -0.006(3) 0.021(3) -0.018(3)
C10 0.097(5) 0.025(3) 0.046(4) 0.000 -0.018(4) 0.000
C4C 0.118(5) 0.133(6) 0.070(4) 0.025(4) 0.003(4) -0.052(5)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O7 1.939(2) . ?
Cu1 O2 1.955(2) . ?
Cu1 O1 1.960(2) . ?
Cu1 O3 1.976(2) . ?
Cu1 O4 2.282(3) . ?
Cu2 O7 1.924(2) . ?
Cu2 O7 1.924(2) 2_556 ?
Cu2 O6 1.943(2) . ?
Cu2 O6 1.943(2) 2_556 ?
180

O1 C1 1.252(4) . ?
O2 C3 1.249(4) . ?
O3 C4 1.279(4) . ?
O5 C7 1.254(4) . ?
O4 C6 1.219(4) . ?
O7 H1O 0.828(19) . ?
O6 C9 1.255(5) . ?
F2 C11 1.351(5) . ?
F3 C15 1.320(4) . ?
F15 C15 1.343(4) . ?
F8 C13 1.332(4) . ?
F6 C12 1.282(5) . ?
F14 C11 1.311(4) . ?
F13 C15 1.322(4) . ?
F1 C11 1.333(5) . ?
F5 C12 1.312(5) . ?
F18 C16 1.313(6) . ?
F7 C13 1.336(5) . ?
F9 C13 1.332(4) . ?
F17 C16 1.326(6) . ?
F16 C16 1.343(6) . ?
F4 C12 1.357(5) . ?
F10 C14 1.305(6) . ?
F12 C14 1.328(6) . ?
F11 C14 1.310(6) . ?
N1C C1C 1.484(5) . ?
N1C C3C 1.520(6) . ?
N1C H1C1 0.9200 . ?
N1C H1C2 0.9200 . ?
C8 C7 1.398(4) 2_556 ?
C8 C7 1.398(4) . ?
C8 H8 0.9500 . ?
C7 C15 1.530(5) . ?
C5 C4 1.366(6) . ?
C5 C6 1.417(6) . ?
C5 H5 0.72(4) . ?
C13 C4 1.529(5) . ?
C1 C2 1.378(5) . ?
C1 C12 1.527(5) . ?
C3 C2 1.389(5) . ?
C3 C11 1.557(5) . ?
C9 C10 1.397(5) . ?
C9 C16 1.532(6) . ?
C6 C14 1.557(6) . ?
181

C1C C2C 1.420(7) . ?

C1C C2C 1.47(3) . ?
C1C H1C1 0.9900 . ?
C1C H1C2 0.9900 . ?
C2 H2 0.9500 . ?
C3C C4C 1.458(7) . ?
C3C H3C1 0.9900 . ?
C3C H3C2 0.9900 . ?
C10 C9 1.397(5) 2_556 ?
C10 H10 0.9500 . ?
C4C H4C1 0.9800 . ?
C4C H4C2 0.9800 . ?
C4C H4C3 0.9800 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O7 Cu1 O2 177.98(10) . . ?
O7 Cu1 O1 87.64(10) . . ?
O2 Cu1 O1 92.15(10) . . ?
O7 Cu1 O3 88.83(10) . . ?
O2 Cu1 O3 91.22(10) . . ?
O1 Cu1 O3 174.45(10) . . ?
O7 Cu1 O4 99.19(10) . . ?
O2 Cu1 O4 82.84(10) . . ?
O1 Cu1 O4 97.93(10) . . ?
O3 Cu1 O4 86.86(10) . . ?
O7 Cu2 O7 92.84(14) . 2_556 ?
O7 Cu2 O6 87.75(10) . . ?
O7 Cu2 O6 179.12(10) 2_556 . ?
O7 Cu2 O6 179.12(11) . 2_556 ?
O7 Cu2 O6 87.75(10) 2_556 2_556 ?
O6 Cu2 O6 91.67(15) . 2_556 ?
C1 O1 Cu1 125.0(2) . . ?
C3 O2 Cu1 124.3(2) . . ?
C4 O3 Cu1 126.7(2) . . ?
C6 O4 Cu1 120.2(2) . . ?
Cu2 O7 Cu1 109.77(11) . . ?
Cu2 O7 H1O 108(3) . . ?
182

Cu1 O7 H1O 103(3) . . ?

C9 O6 Cu2 126.1(3) . . ?
C1C N1C C3C 116.0(4) . . ?
C1C N1C H1C1 108.3 . . ?
C3C N1C H1C1 108.3 . . ?
C1C N1C H1C2 108.3 . . ?
C3C N1C H1C2 108.3 . . ?
H1C1 N1C H1C2 107.4 . . ?
C7 C8 C7 124.1(4) 2_556 . ?
C7 C8 H8 118.0 2_556 . ?
C7 C8 H8 118.0 . . ?
O5 C7 C8 128.7(3) . . ?
O5 C7 C15 113.5(3) . . ?
C8 C7 C15 117.9(3) . . ?
C4 C5 C6 124.3(4) . . ?
C4 C5 H5 115(4) . . ?
C6 C5 H5 121(4) . . ?
F8 C13 F9 108.2(3) . . ?
F8 C13 F7 106.8(3) . . ?
F9 C13 F7 104.8(3) . . ?
F8 C13 C4 113.6(3) . . ?
F9 C13 C4 111.9(3) . . ?
F7 C13 C4 111.1(3) . . ?
O1 C1 C2 127.6(3) . . ?
O1 C1 C12 114.6(3) . . ?
C2 C1 C12 117.8(3) . . ?
O2 C3 C2 128.3(3) . . ?
O2 C3 C11 112.3(3) . . ?
C2 C3 C11 119.2(3) . . ?
F14 C11 F1 108.2(4) . . ?
F14 C11 F2 108.1(3) . . ?
F1 C11 F2 107.7(3) . . ?
F14 C11 C3 113.1(3) . . ?
F1 C11 C3 109.6(3) . . ?
F2 C11 C3 110.0(3) . . ?
F3 C15 F13 107.3(3) . . ?
F3 C15 F15 106.0(3) . . ?
F13 C15 F15 107.2(3) . . ?
F3 C15 C7 111.2(3) . . ?
F13 C15 C7 110.7(3) . . ?
F15 C15 C7 114.0(3) . . ?
O3 C4 C5 129.2(4) . . ?
O3 C4 C13 111.9(3) . . ?
C5 C4 C13 118.9(3) . . ?
183

O6 C9 C10 127.3(4) . . ?
O6 C9 C16 113.3(4) . . ?
C10 C9 C16 119.4(4) . . ?
O4 C6 C5 128.4(4) . . ?
O4 C6 C14 115.7(4) . . ?
C5 C6 C14 115.9(4) . . ?
F6 C12 F5 109.5(4) . . ?
F6 C12 F4 107.8(4) . . ?
F5 C12 F4 102.6(3) . . ?
F6 C12 C1 114.0(3) . . ?
F5 C12 C1 112.6(3) . . ?
F4 C12 C1 109.5(3) . . ?
C2C C1C C2C 47.9(12) . . ?
C2C C1C N1C 112.2(4) . . ?
C2C C1C N1C 139.8(12) . . ?
C2C C1C H1C1 109.2 . . ?
C2C C1C H1C1 110.6 . . ?
N1C C1C H1C1 109.2 . . ?
C2C C1C H1C2 109.2 . . ?
C2C C1C H1C2 63.2 . . ?
N1C C1C H1C2 109.2 . . ?
H1C1 C1C H1C2 107.9 . . ?
C1 C2 C3 122.2(3) . . ?
C1 C2 H2 118.9 . . ?
C3 C2 H2 118.9 . . ?
F10 C14 F11 106.6(4) . . ?
F10 C14 F12 107.4(5) . . ?
F11 C14 F12 106.8(5) . . ?
F10 C14 C6 112.1(4) . . ?
F11 C14 C6 112.6(4) . . ?
F12 C14 C6 111.1(4) . . ?
F18 C16 F17 107.6(4) . . ?
F18 C16 F16 107.9(5) . . ?
F17 C16 F16 106.8(4) . . ?
F18 C16 C9 110.9(4) . . ?
F17 C16 C9 113.4(5) . . ?
F16 C16 C9 110.1(4) . . ?
C4C C3C N1C 114.9(4) . . ?
C4C C3C H3C1 108.6 . . ?
N1C C3C H3C1 108.6 . . ?
C4C C3C H3C2 108.6 . . ?
N1C C3C H3C2 108.6 . . ?
H3C1 C3C H3C2 107.5 . . ?
C9 C10 C9 121.4(5) . 2_556 ?
184

C9 C10 H10 119.3 . . ?

C9 C10 H10 119.3 2_556 . ?
C3C C4C H4C1 109.5 . . ?
C3C C4C H4C2 109.5 . . ?
H4C1 C4C H4C2 109.5 . . ?
C3C C4C H4C3 109.5 . . ?
H4C1 C4C H4C3 109.5 . . ?
H4C2 C4C H4C3 109.5 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O7 Cu1 O1 C1 175.7(3) . . . . ?
O2 Cu1 O1 C1 -2.3(3) . . . . ?
O3 Cu1 O1 C1 125.1(10) . . . . ?
O4 Cu1 O1 C1 -85.4(3) . . . . ?
O7 Cu1 O2 C3 -88(3) . . . . ?
O1 Cu1 O2 C3 -3.5(3) . . . . ?
O3 Cu1 O2 C3 -179.1(3) . . . . ?
O4 Cu1 O2 C3 94.3(3) . . . . ?
O7 Cu1 O3 C4 119.1(3) . . . . ?
O2 Cu1 O3 C4 -62.9(3) . . . . ?
O1 Cu1 O3 C4 169.6(9) . . . . ?
O4 Cu1 O3 C4 19.8(3) . . . . ?
O7 Cu1 O4 C6 -108.8(3) . . . . ?
O2 Cu1 O4 C6 71.1(3) . . . . ?
O1 Cu1 O4 C6 162.3(3) . . . . ?
O3 Cu1 O4 C6 -20.5(3) . . . . ?
O7 Cu2 O7 Cu1 82.08(11) 2_556 . . . ?
O6 Cu2 O7 Cu1 -97.27(12) . . . . ?
O6 Cu2 O7 Cu1 -146(7) 2_556 . . . ?
O2 Cu1 O7 Cu2 -83(3) . . . . ?
O1 Cu1 O7 Cu2 -167.70(12) . . . . ?
O3 Cu1 O7 Cu2 8.02(12) . . . . ?
O4 Cu1 O7 Cu2 94.64(12) . . . . ?
O7 Cu2 O6 C9 -178.1(3) . . . . ?
185

O7 Cu2 O6 C9 50(7) 2_556 . . . ?

O6 Cu2 O6 C9 1.3(3) 2_556 . . . ?
C7 C8 C7 O5 4.3(3) 2_556 . . . ?
C7 C8 C7 C15 -176.2(3) 2_556 . . . ?
Cu1 O1 C1 C2 4.9(5) . . . . ?
Cu1 O1 C1 C12 -176.6(2) . . . . ?
Cu1 O2 C3 C2 7.6(6) . . . . ?
Cu1 O2 C3 C11 -168.0(2) . . . . ?
O2 C3 C11 F14 179.1(3) . . . . ?
C2 C3 C11 F14 3.0(5) . . . . ?
O2 C3 C11 F1 58.3(4) . . . . ?
C2 C3 C11 F1 -117.8(4) . . . . ?
O2 C3 C11 F2 -59.9(4) . . . . ?
C2 C3 C11 F2 124.0(4) . . . . ?
O5 C7 C15 F3 -59.6(4) . . . . ?
C8 C7 C15 F3 120.8(3) . . . . ?
O5 C7 C15 F13 59.5(4) . . . . ?
C8 C7 C15 F13 -120.1(3) . . . . ?
O5 C7 C15 F15 -179.5(3) . . . . ?
C8 C7 C15 F15 0.9(4) . . . . ?
Cu1 O3 C4 C5 -14.7(5) . . . . ?
Cu1 O3 C4 C13 165.1(2) . . . . ?
C6 C5 C4 O3 -0.2(7) . . . . ?
C6 C5 C4 C13 -179.9(4) . . . . ?
F8 C13 C4 O3 171.0(3) . . . . ?
F9 C13 C4 O3 48.1(4) . . . . ?
F7 C13 C4 O3 -68.6(4) . . . . ?
F8 C13 C4 C5 -9.3(5) . . . . ?
F9 C13 C4 C5 -132.1(4) . . . . ?
F7 C13 C4 C5 111.2(4) . . . . ?
Cu2 O6 C9 C10 -2.7(5) . . . . ?
Cu2 O6 C9 C16 177.2(3) . . . . ?
Cu1 O4 C6 C5 15.9(6) . . . . ?
Cu1 O4 C6 C14 -162.1(3) . . . . ?
C4 C5 C6 O4 -2.5(7) . . . . ?
C4 C5 C6 C14 175.5(4) . . . . ?
O1 C1 C12 F6 -6.2(5) . . . . ?
C2 C1 C12 F6 172.5(4) . . . . ?
O1 C1 C12 F5 -131.8(4) . . . . ?
C2 C1 C12 F5 46.9(5) . . . . ?
O1 C1 C12 F4 114.7(4) . . . . ?
C2 C1 C12 F4 -66.6(5) . . . . ?
C3C N1C C1C C2C 168.1(4) . . . . ?
C3C N1C C1C C2C 117.9(19) . . . . ?
186

O1 C1 C2 C3 -1.6(7) . . . . ?
C12 C1 C2 C3 179.9(4) . . . . ?
O2 C3 C2 C1 -5.5(7) . . . . ?
C11 C3 C2 C1 169.9(4) . . . . ?
O4 C6 C14 F10 108.6(5) . . . . ?
C5 C6 C14 F10 -69.7(6) . . . . ?
O4 C6 C14 F11 -131.2(4) . . . . ?
C5 C6 C14 F11 50.5(6) . . . . ?
O4 C6 C14 F12 -11.6(6) . . . . ?
C5 C6 C14 F12 170.2(4) . . . . ?
O6 C9 C16 F18 62.6(5) . . . . ?
C10 C9 C16 F18 -117.5(4) . . . . ?
O6 C9 C16 F17 -176.3(4) . . . . ?
C10 C9 C16 F17 3.6(6) . . . . ?
O6 C9 C16 F16 -56.7(5) . . . . ?
C10 C9 C16 F16 123.2(4) . . . . ?
C1C N1C C3C C4C -76.2(6) . . . . ?
O6 C9 C10 C9 1.5(3) . . . 2_556 ?
C16 C9 C10 C9 -178.4(4) . . . 2_556 ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1C H1C1 F2 0.92 2.48 3.312(4) 150.4 8_556
N1C H1C2 O7 0.92 1.80 2.707(4) 167.0 .
O7 H1O O5 0.828(19) 1.93(2) 2.752(3) 173(4) 2_556
_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full
27.50
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max 0.734
_refine_diff_density_min -0.490
_refine_diff_density_rms 0.081
# END OF CIF

187

Table A-8. CIF File For Cu(hfac)2(CF3COCH(CF3)CHCHN(i-Pr)2)2

_audit_creation_method
_chemical_name_systematic
;

SHELXL-97

trans-bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis(6-diisopropylamino-1,1,1-triflu
oro-4(trifluoromethyl)-(E,E)hexa-3,5-dien-2-one)copper(II)
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety
'C36 H36 Cu F24 N2 O6'
_chemical_formula_sum
'C36 H36 Cu F24 N2 O6'
_chemical_formula_weight
1112.21
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting
triclinic
_symmetry_space_group_name_H-M P-1
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
_cell_length_a

10.735(4)
188

_cell_length_b
10.753(4)
_cell_length_c
11.253(3)
_cell_angle_alpha
95.166(18)
_cell_angle_beta
109.532(19)
_cell_angle_gamma
109.655(16)
_cell_volume
1122.5(7)
_cell_formula_units_Z
1
_cell_measurement_temperature 150
_cell_measurement_reflns_used 17509
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
28.7
_exptl_crystal_description
fragment
_exptl_crystal_colour
'green-brown dichroic'
_exptl_crystal_size_max
0.42
_exptl_crystal_size_mid
0.35
_exptl_crystal_size_min
0.25
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.645
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
559
_exptl_absorpt_coefficient_mu 0.631
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.777
_exptl_absorpt_correction_T_max 0.858
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
150
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
189

_diffrn_reflns_number
17509
_diffrn_reflns_av_R_equivalents 0.022
_diffrn_reflns_av_sigmaI/netI 0.0349
_diffrn_reflns_limit_h_min
-14
_diffrn_reflns_limit_h_max
12
_diffrn_reflns_limit_k_min
-13
_diffrn_reflns_limit_k_max
14
_diffrn_reflns_limit_l_min
-15
_diffrn_reflns_limit_l_max
15
_diffrn_reflns_theta_min
2.8
_diffrn_reflns_theta_max
28.7
_reflns_number_total
5664
_reflns_number_gt
4772
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0688P)^2^+0.2844P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment constr
_refine_ls_extinction_method
none
190

_refine_ls_extinction_coef
?
_refine_ls_number_reflns
5664
_refine_ls_number_parameters
353
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.050
_refine_ls_R_factor_gt
0.043
_refine_ls_wR_factor_ref
0.126
_refine_ls_wR_factor_gt
0.122
_refine_ls_goodness_of_fit_ref 1.109
_refine_ls_restrained_S_all
1.109
_refine_ls_shift/su_max
0.002
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.5000 0.5000 0.5000 0.03012(11) Uani 1 2 d S . .
F1 F 0.80594(17) 0.67994(14) 0.95394(15) 0.0677(4) Uani 1 1 d . . .
F2 F 0.7821(2) 0.47841(18) 0.89705(14) 0.0823(6) Uani 1 1 d . . .
F3 F 0.65755(19) 0.5230(3) 0.99346(16) 0.0934(7) Uani 1 1 d . . .
F4A F 0.1539(9) 0.5923(13) 0.5847(8) 0.094(3) Uani 0.50 1 d P . .
F4B F 0.1434(8) 0.5611(13) 0.5978(10) 0.101(3) Uani 0.50 1 d P . .
F5 F 0.3068(3) 0.7630(2) 0.6833(4) 0.1404(12) Uani 1 1 d . . .
F6A F 0.2763(9) 0.6598(8) 0.7984(7) 0.108(3) Uani 0.50 1 d P . .
F6B F 0.2299(8) 0.5872(7) 0.7796(8) 0.080(2) Uani 0.50 1 d P . .
F7A F 0.0189(7) 0.1074(6) 0.3356(11) 0.176(6) Uani 0.50 1 d P . .
F7B F 0.0610(6) 0.1217(7) 0.2898(5) 0.0817(19) Uani 0.50 1 d P . .
F8 F 0.10797(18) 0.3179(2) 0.3376(2) 0.0939(7) Uani 1 1 d . . .
F9A F 0.0320(8) 0.2699(11) 0.4655(7) 0.140(3) Uani 0.50 1 d P . .
F9B F -0.0113(4) 0.1763(7) 0.4264(5) 0.0783(16) Uani 0.50 1 d P . .
F10 F 0.21068(15) 0.13480(16) 0.82779(13) 0.0557(3) Uani 1 1 d . . .
F11 F 0.43826(15) 0.21608(15) 0.93316(12) 0.0546(3) Uani 1 1 d . . .
F12 F 0.32802(17) 0.00875(13) 0.82761(13) 0.0553(3) Uani 1 1 d . . .
191

O1 O 0.61621(14) 0.50384(13) 0.67756(12) 0.0327(3) Uani 1 1 d . . .

O2 O 0.37156(14) 0.55971(13) 0.55337(12) 0.0332(3) Uani 1 1 d . . .
O3 O 0.34428(14) 0.26555(13) 0.45952(13) 0.0360(3) Uani 1 1 d . . .
N1 N 0.71722(17) 0.16782(15) 0.77617(15) 0.0325(3) Uani 1 1 d . . .
C1 C 0.7114(2) 0.55420(19) 0.90591(18) 0.0379(4) Uani 1 1 d . . .
C2 C 0.59611(19) 0.54317(17) 0.77472(16) 0.0302(3) Uani 1 1 d . . .
C3 C 0.4864(2) 0.5820(2) 0.77991(18) 0.0378(4) Uani 1 1 d . . .
H3 H 0.4819 0.6055 0.8614 0.045 Uiso 1 1 calc R . .
C4 C 0.3839(2) 0.58703(18) 0.66886(17) 0.0324(4) Uani 1 1 d . . .
C5 C 0.2694(3) 0.6344(3) 0.6842(2) 0.0504(5) Uani 1 1 d . . .
C6 C 0.0986(2) 0.2208(3) 0.3973(3) 0.0522(6) Uani 1 1 d . . .
C7 C 0.2432(2) 0.23044(19) 0.49654(19) 0.0363(4) Uani 1 1 d . . .
C8 C 0.2430(2) 0.19320(19) 0.61287(19) 0.0365(4) Uani 1 1 d . . .
H8 H 0.1593 0.1790 0.6305 0.044 Uiso 1 1 calc R . .
C9 C 0.3570(2) 0.17570(17) 0.70416(17) 0.0329(4) Uani 1 1 d . . .
C10 C 0.3323(2) 0.1336(2) 0.82243(19) 0.0408(4) Uani 1 1 d . . .
C11 C 0.48715(19) 0.19009(17) 0.69404(17) 0.0317(4) Uani 1 1 d . . .
H11 H 0.5044 0.2237 0.6234 0.038 Uiso 1 1 calc R . .
C12 C 0.5931(2) 0.15853(18) 0.78061(17) 0.0326(4) Uani 1 1 d . . .
H12 H 0.5739 0.1265 0.8512 0.039 Uiso 1 1 calc R . .
C13 C 0.7643(2) 0.2176(2) 0.67325(18) 0.0364(4) Uani 1 1 d . . .
H13 H 0.6964 0.2567 0.6230 0.044 Uiso 1 1 calc R . .
C14 C 0.9136(3) 0.3280(3) 0.7285(3) 0.0593(6) Uani 1 1 d . . .
H14A H 0.9221 0.3939 0.7998 0.089 Uiso 1 1 calc R . .
H14B H 0.9310 0.3737 0.6607 0.089 Uiso 1 1 calc R . .
H14C H 0.9844 0.2879 0.7608 0.089 Uiso 1 1 calc R . .
C15 C 0.7549(5) 0.1006(3) 0.5818(3) 0.0908(12) Uani 1 1 d . . .
H15A H 0.8167 0.0574 0.6297 0.136 Uiso 1 1 calc R . .
H15B H 0.7865 0.1339 0.5142 0.136 Uiso 1 1 calc R . .
H15C H 0.6554 0.0343 0.5418 0.136 Uiso 1 1 calc R . .
C16 C 0.8095(2) 0.1171(2) 0.8736(2) 0.0433(5) Uani 1 1 d . . .
H16 H 0.8983 0.1323 0.8561 0.052 Uiso 1 1 calc R . .
C17 C 0.8553(3) 0.1979(3) 1.0099(2) 0.0576(6) Uani 1 1 d . . .
H17A H 0.9022 0.2947 1.0146 0.086 Uiso 1 1 calc R . .
H17B H 0.9225 0.1687 1.0719 0.086 Uiso 1 1 calc R . .
H17C H 0.7706 0.1822 1.0311 0.086 Uiso 1 1 calc R . .
C18 C 0.7337(3) -0.0353(3) 0.8578(3) 0.0605(7) Uani 1 1 d . . .
H18A H 0.6502 -0.0528 0.8811 0.091 Uiso 1 1 calc R . .
H18B H 0.8002 -0.0691 0.9145 0.091 Uiso 1 1 calc R . .
H18C H 0.7020 -0.0819 0.7675 0.091 Uiso 1 1 calc R . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
192

_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.03177(17) 0.04016(18) 0.02510(16) 0.00962(12) 0.01228(12) 0.02018(14)
F1 0.0579(9) 0.0475(7) 0.0576(8) 0.0018(6) -0.0140(7) 0.0118(7)
F2 0.1021(13) 0.0886(11) 0.0476(8) -0.0085(8) -0.0142(8) 0.0761(11)
F3 0.0635(10) 0.170(2) 0.0514(9) 0.0657(12) 0.0221(8) 0.0416(12)
F4A 0.086(6) 0.196(9) 0.039(2) 0.015(4) 0.017(3) 0.112(6)
F4B 0.030(3) 0.143(6) 0.105(7) -0.025(5) 0.023(3) 0.023(3)
F5 0.124(2) 0.0808(14) 0.260(4) 0.0315(18) 0.092(2) 0.0756(15)
F6A 0.142(7) 0.216(9) 0.0378(18) 0.025(4) 0.040(3) 0.149(7)
F6B 0.085(4) 0.142(5) 0.077(4) 0.061(4) 0.064(4) 0.079(4)
F7A 0.059(4) 0.048(2) 0.270(12) 0.011(5) -0.084(6) -0.005(3)
F7B 0.056(3) 0.111(5) 0.0500(18) -0.021(2) -0.0147(18) 0.044(3)
F8 0.0532(10) 0.0929(13) 0.1088(15) 0.0582(12) -0.0020(9) 0.0212(9)
F9A 0.115(6) 0.283(10) 0.108(5) 0.077(6) 0.055(4) 0.161(7)
F9B 0.0284(16) 0.139(5) 0.074(3) 0.047(3) 0.0225(18) 0.032(3)
F10 0.0504(8) 0.0732(9) 0.0522(8) 0.0135(7) 0.0331(7) 0.0216(7)
F11 0.0550(8) 0.0650(8) 0.0331(6) -0.0023(6) 0.0180(6) 0.0133(7)
F12 0.0759(9) 0.0458(7) 0.0567(8) 0.0229(6) 0.0402(7) 0.0214(7)
O1 0.0343(7) 0.0391(6) 0.0283(6) 0.0100(5) 0.0111(5) 0.0193(6)
O2 0.0338(7) 0.0431(7) 0.0286(6) 0.0081(5) 0.0132(5) 0.0208(6)
O3 0.0326(7) 0.0373(7) 0.0407(7) 0.0132(5) 0.0146(6) 0.0153(5)
N1 0.0355(8) 0.0351(7) 0.0311(7) 0.0137(6) 0.0137(6) 0.0164(6)
C1 0.0429(10) 0.0370(9) 0.0301(9) 0.0064(7) 0.0084(8) 0.0174(8)
C2 0.0336(9) 0.0259(7) 0.0275(8) 0.0075(6) 0.0085(7) 0.0102(7)
C3 0.0455(11) 0.0456(10) 0.0273(8) 0.0072(7) 0.0141(8) 0.0241(9)
C4 0.0357(9) 0.0332(8) 0.0317(8) 0.0059(7) 0.0146(7) 0.0162(7)
C5 0.0561(14) 0.0703(15) 0.0397(11) 0.0098(10) 0.0208(10) 0.0410(12)
C6 0.0325(11) 0.0554(13) 0.0671(15) 0.0244(11) 0.0132(10) 0.0186(10)
C7 0.0306(9) 0.0328(9) 0.0437(10) 0.0068(7) 0.0115(8) 0.0136(7)
C8 0.0314(9) 0.0359(9) 0.0423(10) 0.0045(8) 0.0173(8) 0.0114(7)
C9 0.0361(9) 0.0278(8) 0.0325(8) 0.0029(7) 0.0158(7) 0.0085(7)
C10 0.0430(11) 0.0419(10) 0.0366(10) 0.0051(8) 0.0202(9) 0.0119(8)
C11 0.0331(9) 0.0307(8) 0.0313(8) 0.0079(7) 0.0129(7) 0.0117(7)
C12 0.0380(9) 0.0307(8) 0.0292(8) 0.0076(7) 0.0141(7) 0.0124(7)
C13 0.0381(10) 0.0426(10) 0.0343(9) 0.0180(8) 0.0166(8) 0.0179(8)
C14 0.0511(14) 0.0603(14) 0.0633(15) 0.0143(12) 0.0321(12) 0.0082(11)
C15 0.145(3) 0.0570(16) 0.0646(18) -0.0004(13) 0.071(2) 0.0058(18)
C16 0.0454(11) 0.0565(12) 0.0410(10) 0.0258(9) 0.0185(9) 0.0298(10)
C17 0.0520(14) 0.0772(17) 0.0364(11) 0.0201(11) 0.0075(10) 0.0245(12)
C18 0.0854(19) 0.0567(14) 0.0646(15) 0.0369(12) 0.0376(14) 0.0433(14)
193

_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O2 1.9374(12) . ?
Cu1 O2 1.9374(12) 2_666 ?
Cu1 O1 1.9581(12) . ?
Cu1 O1 1.9581(12) 2_666 ?
Cu1 O3 2.4097(13) . ?
Cu1 O3 2.4097(13) 2_666 ?
F1 C1 1.315(2) . ?
F2 C1 1.305(2) . ?
F3 C1 1.314(3) . ?
F4A C5 1.264(8) . ?
F4B C5 1.289(9) . ?
F5 C5 1.305(3) . ?
F6A F6B 0.736(11) . ?
F6A C5 1.261(7) . ?
F6B C5 1.360(7) . ?
F7A F7B 0.785(14) . ?
F7A C6 1.204(7) . ?
F7A F9B 1.394(12) . ?
F7B C6 1.383(6) . ?
F8 C6 1.285(3) . ?
F9A F9B 0.944(9) . ?
F9A C6 1.388(7) . ?
F9B C6 1.278(5) . ?
F10 C10 1.331(2) . ?
F11 C10 1.345(2) . ?
F12 C10 1.335(2) . ?
O1 C2 1.248(2) . ?
O2 C4 1.258(2) . ?
194

O3 C7 1.244(2) . ?
N1 C12 1.320(2) . ?
N1 C13 1.485(2) . ?
N1 C16 1.492(2) . ?
C1 C2 1.540(2) . ?
C2 C3 1.392(3) . ?
C3 C4 1.381(3) . ?
C3 H3 0.9500 . ?
C4 C5 1.532(3) . ?
C6 C7 1.543(3) . ?
C7 C8 1.403(3) . ?
C8 C9 1.392(3) . ?
C8 H8 0.9500 . ?
C9 C11 1.397(3) . ?
C9 C10 1.520(3) . ?
C11 C12 1.392(3) . ?
C11 H11 0.9500 . ?
C12 H12 0.9500 . ?
C13 C15 1.505(3) . ?
C13 C14 1.512(3) . ?
C13 H13 1.0000 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C16 C17 1.523(3) . ?
C16 C18 1.527(3) . ?
C16 H16 1.0000 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
195

_geom_angle_publ_flag
O2 Cu1 O2 180.00(3) . 2_666 ?
O2 Cu1 O1 92.88(5) . . ?
O2 Cu1 O1 87.12(5) 2_666 . ?
O2 Cu1 O1 87.11(5) . 2_666 ?
O2 Cu1 O1 92.89(5) 2_666 2_666 ?
O1 Cu1 O1 180.0 . 2_666 ?
O2 Cu1 O3 91.32(5) . . ?
O2 Cu1 O3 88.68(5) 2_666 . ?
O1 Cu1 O3 93.12(5) . . ?
O1 Cu1 O3 86.88(5) 2_666 . ?
O2 Cu1 O3 88.69(5) . 2_666 ?
O2 Cu1 O3 91.32(5) 2_666 2_666 ?
O1 Cu1 O3 86.88(5) . 2_666 ?
O1 Cu1 O3 93.12(5) 2_666 2_666 ?
O3 Cu1 O3 180.00(4) . 2_666 ?
F6B F6A C5 81.2(10) . . ?
F6A F6B C5 66.4(9) . . ?
F7B F7A C6 85.3(9) . . ?
F7B F7A F9B 140.5(11) . . ?
C6 F7A F9B 58.4(5) . . ?
F7A F7B C6 60.2(7) . . ?
F9B F9A C6 63.2(5) . . ?
F9A F9B C6 75.6(6) . . ?
F9A F9B F7A 127.7(8) . . ?
C6 F9B F7A 53.3(3) . . ?
C2 O1 Cu1 124.01(12) . . ?
C4 O2 Cu1 124.37(12) . . ?
C7 O3 Cu1 122.03(12) . . ?
C12 N1 C13 122.90(15) . . ?
C12 N1 C16 118.43(15) . . ?
C13 N1 C16 118.53(15) . . ?
F2 C1 F3 108.23(19) . . ?
F2 C1 F1 107.05(19) . . ?
F3 C1 F1 105.57(19) . . ?
F2 C1 C2 112.85(16) . . ?
F3 C1 C2 112.49(17) . . ?
F1 C1 C2 110.25(15) . . ?
O1 C2 C3 128.61(16) . . ?
O1 C2 C1 115.13(16) . . ?
C3 C2 C1 116.22(16) . . ?
C4 C3 C2 121.26(17) . . ?
C4 C3 H3 119.4 . . ?
C2 C3 H3 119.4 . . ?
196

O2 C4 C3 128.72(17) . . ?
O2 C4 C5 113.63(16) . . ?
C3 C4 C5 117.64(17) . . ?
F6A C5 F4A 123.9(6) . . ?
F6A C5 F4B 115.5(7) . . ?
F4A C5 F4B 16.9(10) . . ?
F6A C5 F5 90.3(4) . . ?
F4A C5 F5 96.6(6) . . ?
F4B C5 F5 112.5(6) . . ?
F6A C5 F6B 32.3(5) . . ?
F4A C5 F6B 105.0(6) . . ?
F4B C5 F6B 91.1(6) . . ?
F5 C5 F6B 120.4(3) . . ?
F6A C5 C4 115.5(4) . . ?
F4A C5 C4 114.2(5) . . ?
F4B C5 C4 111.8(5) . . ?
F5 C5 C4 109.4(2) . . ?
F6B C5 C4 110.6(4) . . ?
F7A C6 F9B 68.3(6) . . ?
F7A C6 F8 118.1(5) . . ?
F9B C6 F8 117.0(3) . . ?
F7A C6 F7B 34.5(7) . . ?
F9B C6 F7B 101.5(4) . . ?
F8 C6 F7B 95.3(4) . . ?
F7A C6 F9A 108.7(7) . . ?
F9B C6 F9A 41.2(4) . . ?
F8 C6 F9A 91.0(4) . . ?
F7B C6 F9A 138.7(5) . . ?
F7A C6 C7 113.9(4) . . ?
F9B C6 C7 117.4(3) . . ?
F8 C6 C7 114.48(19) . . ?
F7B C6 C7 106.9(3) . . ?
F9A C6 C7 107.4(3) . . ?
O3 C7 C8 128.49(18) . . ?
O3 C7 C6 114.65(18) . . ?
C8 C7 C6 116.79(18) . . ?
C9 C8 C7 124.51(17) . . ?
C9 C8 H8 117.7 . . ?
C7 C8 H8 117.7 . . ?
C8 C9 C11 125.84(17) . . ?
C8 C9 C10 115.41(17) . . ?
C11 C9 C10 118.74(17) . . ?
F10 C10 F12 106.70(17) . . ?
F10 C10 F11 106.21(16) . . ?
197

F12 C10 F11 106.17(18) . . ?

F10 C10 C9 113.62(18) . . ?
F12 C10 C9 111.97(16) . . ?
F11 C10 C9 111.69(17) . . ?
C12 C11 C9 124.35(17) . . ?
C12 C11 H11 117.8 . . ?
C9 C11 H11 117.8 . . ?
N1 C12 C11 127.62(17) . . ?
N1 C12 H12 116.2 . . ?
C11 C12 H12 116.2 . . ?
N1 C13 C15 109.70(17) . . ?
N1 C13 C14 112.10(17) . . ?
C15 C13 C14 111.2(2) . . ?
N1 C13 H13 107.9 . . ?
C15 C13 H13 107.9 . . ?
C14 C13 H13 107.9 . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
N1 C16 C17 110.53(18) . . ?
N1 C16 C18 110.56(19) . . ?
C17 C16 C18 112.78(19) . . ?
N1 C16 H16 107.6 . . ?
C17 C16 H16 107.6 . . ?
C18 C16 H16 107.6 . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C16 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C16 C18 H18A 109.5 . . ?
C16 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C16 C18 H18C 109.5 . . ?
198

H18A C18 H18C 109.5 . . ?

H18B C18 H18C 109.5 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
F9B F7A F7B C6 22.3(13) . . . . ?
C6 F9A F9B F7A -12.1(8) . . . . ?
F7B F7A F9B F9A -12(2) . . . . ?
C6 F7A F9B F9A 14.7(10) . . . . ?
F7B F7A F9B C6 -26.4(15) . . . . ?
O2 Cu1 O1 C2 -3.44(14) . . . . ?
O2 Cu1 O1 C2 176.56(14) 2_666 . . . ?
O1 Cu1 O1 C2 15(10) 2_666 . . . ?
O3 Cu1 O1 C2 -94.92(14) . . . . ?
O3 Cu1 O1 C2 85.08(14) 2_666 . . . ?
O2 Cu1 O2 C4 77(13) 2_666 . . . ?
O1 Cu1 O2 C4 1.01(15) . . . . ?
O1 Cu1 O2 C4 -178.99(15) 2_666 . . . ?
O3 Cu1 O2 C4 94.20(15) . . . . ?
O3 Cu1 O2 C4 -85.80(15) 2_666 . . . ?
O2 Cu1 O3 C7 -12.01(15) . . . . ?
O2 Cu1 O3 C7 167.99(15) 2_666 . . . ?
O1 Cu1 O3 C7 80.95(15) . . . . ?
O1 Cu1 O3 C7 -99.05(15) 2_666 . . . ?
O3 Cu1 O3 C7 -126(12) 2_666 . . . ?
Cu1 O1 C2 C3 5.0(3) . . . . ?
Cu1 O1 C2 C1 -172.79(11) . . . . ?
F2 C1 C2 O1 -22.6(3) . . . . ?
F3 C1 C2 O1 -145.43(19) . . . . ?
F1 C1 C2 O1 97.0(2) . . . . ?
F2 C1 C2 C3 159.27(19) . . . . ?
F3 C1 C2 C3 36.5(3) . . . . ?
F1 C1 C2 C3 -81.1(2) . . . . ?
O1 C2 C3 C4 -3.2(3) . . . . ?
C1 C2 C3 C4 174.59(17) . . . . ?
Cu1 O2 C4 C3 0.2(3) . . . . ?
199

Cu1 O2 C4 C5 178.93(14) . . . . ?
C2 C3 C4 O2 0.2(3) . . . . ?
C2 C3 C4 C5 -178.44(19) . . . . ?
F6B F6A C5 F4A 61.4(14) . . . . ?
F6B F6A C5 F4B 44.3(14) . . . . ?
F6B F6A C5 F5 159.5(11) . . . . ?
F6B F6A C5 C4 -88.7(12) . . . . ?
F6A F6B C5 F4A -131.0(12) . . . . ?
F6A F6B C5 F4B -140.9(13) . . . . ?
F6A F6B C5 F5 -23.9(13) . . . . ?
F6A F6B C5 C4 105.3(11) . . . . ?
O2 C4 C5 F6A 178.4(5) . . . . ?
C3 C4 C5 F6A -2.7(5) . . . . ?
O2 C4 C5 F4A 25.4(7) . . . . ?
C3 C4 C5 F4A -155.7(6) . . . . ?
O2 C4 C5 F4B 43.7(6) . . . . ?
C3 C4 C5 F4B -137.5(6) . . . . ?
O2 C4 C5 F5 -81.5(3) . . . . ?
C3 C4 C5 F5 97.3(3) . . . . ?
O2 C4 C5 F6B 143.6(4) . . . . ?
C3 C4 C5 F6B -37.5(4) . . . . ?
F7B F7A C6 F9B 163.5(11) . . . . ?
F7B F7A C6 F8 53.6(10) . . . . ?
F9B F7A C6 F8 -109.9(5) . . . . ?
F9B F7A C6 F7B -163.5(11) . . . . ?
F7B F7A C6 F9A 155.2(9) . . . . ?
F9B F7A C6 F9A -8.3(6) . . . . ?
F7B F7A C6 C7 -85.1(10) . . . . ?
F9B F7A C6 C7 111.4(4) . . . . ?
F9A F9B C6 F7A -168.1(8) . . . . ?
F9A F9B C6 F8 -56.6(7) . . . . ?
F7A F9B C6 F8 111.5(6) . . . . ?
F9A F9B C6 F7B -158.6(6) . . . . ?
F7A F9B C6 F7B 9.4(7) . . . . ?
F7A F9B C6 F9A 168.1(8) . . . . ?
F9A F9B C6 C7 85.4(7) . . . . ?
F7A F9B C6 C7 -106.6(5) . . . . ?
F7A F7B C6 F9B -15.6(10) . . . . ?
F7A F7B C6 F8 -134.5(9) . . . . ?
F7A F7B C6 F9A -37.0(13) . . . . ?
F7A F7B C6 C7 107.9(9) . . . . ?
F9B F9A C6 F7A 11.7(8) . . . . ?
F9B F9A C6 F8 131.9(6) . . . . ?
F9B F9A C6 F7B 32.8(10) . . . . ?
200

F9B F9A C6 C7 -112.0(6) . . . . ?

Cu1 O3 C7 C8 -92.2(2) . . . . ?
Cu1 O3 C7 C6 90.99(18) . . . . ?
F7A C6 C7 O3 98.4(8) . . . . ?
F9B C6 C7 O3 175.3(4) . . . . ?
F8 C6 C7 O3 -41.8(3) . . . . ?
F7B C6 C7 O3 62.3(4) . . . . ?
F9A C6 C7 O3 -141.2(5) . . . . ?
F7A C6 C7 C8 -78.8(8) . . . . ?
F9B C6 C7 C8 -1.9(5) . . . . ?
F8 C6 C7 C8 141.0(2) . . . . ?
F7B C6 C7 C8 -114.9(4) . . . . ?
F9A C6 C7 C8 41.6(5) . . . . ?
O3 C7 C8 C9 -7.0(3) . . . . ?
C6 C7 C8 C9 169.73(18) . . . . ?
C7 C8 C9 C11 -1.0(3) . . . . ?
C7 C8 C9 C10 -179.33(17) . . . . ?
C8 C9 C10 F10 -7.3(2) . . . . ?
C11 C9 C10 F10 174.30(16) . . . . ?
C8 C9 C10 F12 113.7(2) . . . . ?
C11 C9 C10 F12 -64.7(2) . . . . ?
C8 C9 C10 F11 -127.40(19) . . . . ?
C11 C9 C10 F11 54.2(2) . . . . ?
C8 C9 C11 C12 -173.14(18) . . . . ?
C10 C9 C11 C12 5.1(3) . . . . ?
C13 N1 C12 C11 0.8(3) . . . . ?
C16 N1 C12 C11 -174.83(18) . . . . ?
C9 C11 C12 N1 179.03(18) . . . . ?
C12 N1 C13 C15 -106.8(3) . . . . ?
C16 N1 C13 C15 68.8(3) . . . . ?
C12 N1 C13 C14 129.1(2) . . . . ?
C16 N1 C13 C14 -55.3(2) . . . . ?
C12 N1 C16 C17 -62.6(2) . . . . ?
C13 N1 C16 C17 121.6(2) . . . . ?
C12 N1 C16 C18 63.0(2) . . . . ?
C13 N1 C16 C18 -112.8(2) . . . . ?
_diffrn_measured_fraction_theta_max 0.975
_diffrn_reflns_theta_full
28.71
_diffrn_measured_fraction_theta_full 0.975
_refine_diff_density_max 0.59
_refine_diff_density_min -0.50
_refine_diff_density_rms 0.057
# END OF CIF
201

Table A-9. CIF File For[(hfac)Cu(:3-OCH2CH(OH)CH3)]4

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
bis(bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis(mu2-(2-hydroxypropoxy))dicopp
er(II))
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety 'C32 H32 Cu4 F24 O16'
_chemical_formula_sum
'C32 H32 Cu4 F24 O16'
_chemical_formula_weight
1382.74
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'O' 'O' 0.0106 0.0060
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_space_group_name_H-M 'P 2/c '
_symmetry_cell_setting 'Monoclinic'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
_cell_length_a
_cell_length_b
_cell_length_c

24.046(8)
10.014(3)
23.767(8)
202

_cell_angle_alpha
90
_cell_angle_beta
118.793(15)
_cell_angle_gamma
90
_cell_volume
5015(3)
_cell_formula_units_Z
4
_cell_measurement_temperature 100
_cell_measurement_reflns_used 42761
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
32.0
_exptl_crystal_description
needle
_exptl_crystal_colour
'blue-green'
_exptl_crystal_size_max
0.27
_exptl_crystal_size_mid
0.10
_exptl_crystal_size_min
0.05
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.831
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
2736
_exptl_absorpt_coefficient_mu 1.823
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.639
_exptl_absorpt_correction_T_max 0.914
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
100
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
_diffrn_reflns_number
42761
_diffrn_reflns_av_R_equivalents 0.032
_diffrn_reflns_av_sigmaI/netI 0.2409
203

_diffrn_reflns_limit_h_min -31
_diffrn_reflns_limit_h_max 32
_diffrn_reflns_limit_k_min -12
_diffrn_reflns_limit_k_max 14
_diffrn_reflns_limit_l_min -35
_diffrn_reflns_limit_l_max 35
_diffrn_reflns_theta_min
2.5
_diffrn_reflns_theta_max
32.0
_reflns_number_total
13365
_reflns_number_gt
4711
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution ?
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0719P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment constr
_refine_ls_extinction_method
none
_refine_ls_extinction_coef
?
_refine_ls_number_reflns
13365
_refine_ls_number_parameters
705
204

_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.175
_refine_ls_R_factor_gt
0.060
_refine_ls_wR_factor_ref
0.163
_refine_ls_wR_factor_gt
0.147
_refine_ls_goodness_of_fit_ref 0.880
_refine_ls_restrained_S_all
0.880
_refine_ls_shift/su_max
0.012
_refine_ls_shift/su_mean
0.002
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1A Cu 0.43728(3) 0.54465(7) 0.19075(3) 0.0402(2) Uani 1 1 d . . .
Cu2A Cu 0.53039(3) 0.78971(7) 0.20855(3) 0.0437(2) Uani 1 1 d . . .
F1A F 0.3694(2) 0.2973(5) 0.0044(2) 0.0969(15) Uani 1 1 d . . .
F2A F 0.3877(2) 0.4933(5) -0.0209(2) 0.0906(15) Uani 1 1 d . . .
F3A F 0.2928(2) 0.4262(5) -0.05127(18) 0.0903(14) Uani 1 1 d . . .
F4A F 0.23755(17) 0.5406(4) 0.1681(2) 0.0852(13) Uani 1 1 d . . .
F5A F 0.18997(18) 0.5253(5) 0.0669(2) 0.0926(15) Uani 1 1 d . . .
F6A F 0.23172(19) 0.7104(5) 0.1132(2) 0.0987(16) Uani 1 1 d . . .
F7A F 0.51592(19) 0.8626(4) -0.01675(19) 0.0848(13) Uani 1 1 d . . .
F8A F 0.4320(2) 0.8528(5) -0.00689(19) 0.0984(16) Uani 1 1 d . . .
F9A F 0.4828(3) 0.6745(5) -0.0044(2) 0.1128(18) Uani 1 1 d . . .
F10A F 0.7189(2) 0.8878(5) 0.1648(2) 0.1061(17) Uani 1 1 d . . .
F11A F 0.7200(2) 0.9598(7) 0.2475(3) 0.140(2) Uani 1 1 d . . .
F12A F 0.7347(2) 0.7615(8) 0.2409(3) 0.158(3) Uani 1 1 d . . .
O1A O 0.52721(16) 0.5567(3) 0.21614(16) 0.0354(9) Uani 1 1 d . . .
O2A O 0.44641(16) 0.7819(3) 0.20114(17) 0.0376(9) Uani 1 1 d . . .
O3A O 0.5598(2) 0.3063(5) 0.2532(3) 0.0846(16) Uani 1 1 d . . .
O4A O 0.4360(2) 1.0453(5) 0.2237(3) 0.0986(18) Uani 1 1 d . . .
O5A O 0.41276(18) 0.4940(4) 0.10390(18) 0.0497(11) Uani 1 1 d . . .
O6A O 0.34918(17) 0.5612(3) 0.17234(18) 0.0406(10) Uani 1 1 d . . .
205

O7A O 0.49637(19) 0.7955(4) 0.11569(18) 0.0493(11) Uani 1 1 d . . .

O8A O 0.61634(18) 0.8148(4) 0.2238(2) 0.0505(11) Uani 1 1 d . . .
C1A C 0.5571(3) 0.4812(5) 0.1860(3) 0.0455(16) Uani 1 1 d . . .
H1A1 H 0.6024 0.5065 0.2054 0.055 Uiso 1 1 calc R . .
H1A2 H 0.5365 0.5032 0.1397 0.055 Uiso 1 1 calc R . .
C2A C 0.5519(4) 0.3328(6) 0.1940(3) 0.065(2) Uani 1 1 d . . .
H2A H 0.5077 0.3055 0.1623 0.078 Uiso 1 1 calc R . .
C3A C 0.5964(3) 0.2558(7) 0.1778(3) 0.071(2) Uani 1 1 d . . .
H3A1 H 0.5914 0.1599 0.1821 0.106 Uiso 1 1 calc R . .
H3A2 H 0.6403 0.2821 0.2071 0.106 Uiso 1 1 calc R . .
H3A3 H 0.5864 0.2757 0.1335 0.106 Uiso 1 1 calc R . .
C4A C 0.3947(3) 0.8580(5) 0.1537(3) 0.0469(16) Uani 1 1 d . . .
H4A1 H 0.3570 0.8469 0.1598 0.056 Uiso 1 1 calc R . .
H4A2 H 0.3837 0.8246 0.1104 0.056 Uiso 1 1 calc R . .
C5A C 0.4119(3) 1.0032(6) 0.1587(3) 0.068(2) Uani 1 1 d . . .
H5A H 0.4457 1.0153 0.1460 0.081 Uiso 1 1 calc R . .
C6A C 0.3541(4) 1.0924(7) 0.1153(4) 0.097(3) Uani 1 1 d . . .
H6A1 H 0.3677 1.1857 0.1192 0.146 Uiso 1 1 calc R . .
H6A2 H 0.3216 1.0841 0.1287 0.146 Uiso 1 1 calc R . .
H6A3 H 0.3364 1.0636 0.0705 0.146 Uiso 1 1 calc R . .
C7A C 0.3523(4) 0.4265(8) -0.0032(3) 0.070(2) Uani 1 1 d . . .
C8A C 0.3558(3) 0.4769(6) 0.0603(3) 0.0500(17) Uani 1 1 d . . .
C9A C 0.3008(3) 0.5044(6) 0.0633(3) 0.0536(18) Uani 1 1 d . . .
H9A H 0.2611 0.4947 0.0255 0.064 Uiso 1 1 calc R . .
C10A C 0.3012(3) 0.5445(6) 0.1180(3) 0.0460(16) Uani 1 1 d . . .
C11A C 0.2387(3) 0.5775(8) 0.1148(4) 0.064(2) Uani 1 1 d . . .
C12A C 0.4893(4) 0.8024(9) 0.0152(4) 0.079(2) Uani 1 1 d . . .
C13A C 0.5283(3) 0.8117(6) 0.0872(3) 0.0509(17) Uani 1 1 d . . .
C14A C 0.5930(3) 0.8359(6) 0.1144(3) 0.0528(17) Uani 1 1 d . . .
H14A H 0.6108 0.8530 0.0871 0.063 Uiso 1 1 calc R . .
C15A C 0.6321(3) 0.8359(6) 0.1799(4) 0.0491(17) Uani 1 1 d . . .
C16A C 0.7018(4) 0.8569(10) 0.2074(4) 0.077(2) Uani 1 1 d . . .
Cu1B Cu 0.06706(3) 0.13963(6) 0.26311(3) 0.0378(2) Uani 1 1 d . . .
Cu2B Cu 0.02276(3) -0.10306(7) 0.31959(3) 0.0378(2) Uani 1 1 d . . .
F1B F 0.14040(19) 0.3020(4) 0.13268(19) 0.0805(13) Uani 1 1 d . . .
F2B F 0.23563(19) 0.2376(5) 0.19103(19) 0.0905(14) Uani 1 1 d . . .
F3B F 0.1635(2) 0.0931(5) 0.13736(19) 0.0867(13) Uani 1 1 d . . .
F4B F 0.2737(2) 0.0718(6) 0.4355(2) 0.119(2) Uani 1 1 d . . .
F5B F 0.2398(2) 0.2619(6) 0.4465(2) 0.133(2) Uani 1 1 d . . .
F6B F 0.3035(2) 0.2569(5) 0.4116(2) 0.1142(18) Uani 1 1 d . . .
F7B F 0.2036(2) -0.2206(5) 0.54736(19) 0.0979(16) Uani 1 1 d . . .
F8B F 0.2067(2) -0.0204(5) 0.5189(2) 0.1103(17) Uani 1 1 d . . .
F9B F 0.2240(2) -0.1832(5) 0.4716(2) 0.0986(16) Uani 1 1 d . . .
F10B F -0.0733(4) -0.2952(10) 0.4222(4) 0.219(5) Uani 1 1 d . . .
206

F11B F -0.0685(5) -0.1020(9) 0.4538(6) 0.252(6) Uani 1 1 d . . .

F12B F -0.0083(4) -0.2506(13) 0.5085(4) 0.264(6) Uani 1 1 d . . .
O1B O 0.05764(16) -0.0937(3) 0.26045(16) 0.0336(9) Uani 1 1 d . . .
O2B O 0.01927(16) 0.1293(3) 0.30964(15) 0.0350(9) Uani 1 1 d . . .
O31B O 0.0669(4) -0.3516(6) 0.2986(4) 0.071(4) Uani 0.615(12) 1 d P . .
O32B O 0.0418(6) -0.3517(10) 0.2253(7) 0.057(5) Uani 0.385(12) 1 d P . .
O41B O 0.0567(5) 0.3826(7) 0.3117(4) 0.054(4) Uani 0.538(13) 1 d P . .
O42B O -0.0113(9) 0.3854(10) 0.3039(7) 0.112(8) Uani 0.462(13) 1 d P . .
O5B O 0.1055(2) 0.1616(4) 0.20839(19) 0.0520(11) Uani 1 1 d . . .
O6B O 0.1486(2) 0.1532(4) 0.34072(18) 0.0506(11) Uani 1 1 d . . .
O7B O 0.10633(18) -0.1115(4) 0.39342(19) 0.0484(11) Uani 1 1 d . . .
O8B O -0.01851(19) -0.1358(4) 0.3713(2) 0.0539(11) Uani 1 1 d . . .
C1B C 0.1108(2) -0.1709(5) 0.2713(3) 0.0339(13) Uani 1 1 d . . .
H1B1 H 0.1463 -0.1486 0.3142 0.041 Uiso 1 1 calc R . .
H1B2 H 0.1239 -0.1465 0.2390 0.041 Uiso 1 1 calc R . .
C2B C 0.0993(4) -0.3193(7) 0.2680(5) 0.068(2) Uani 1 1 d . . .
C3B C 0.1544(3) -0.4068(7) 0.2811(4) 0.079(2) Uani 1 1 d . . .
C4B C 0.0380(3) 0.2091(6) 0.3672(3) 0.0449(16) Uani 1 1 d . . .
H4B1 H 0.0817 0.1842 0.3995 0.054 Uiso 1 1 calc R . .
H4B2 H 0.0096 0.1879 0.3852 0.054 Uiso 1 1 calc R . .
C5B C 0.0357(4) 0.3526(7) 0.3552(3) 0.063(2) Uani 1 1 d . . .
C6B C 0.0617(5) 0.4345(8) 0.4146(4) 0.115(4) Uani 1 1 d . . .
C7B C 0.1763(3) 0.2061(9) 0.1710(4) 0.070(2) Uani 1 1 d . . .
C8B C 0.1635(3) 0.1901(6) 0.2265(3) 0.0454(16) Uani 1 1 d . . .
C9B C 0.2097(3) 0.2055(6) 0.2899(4) 0.0553(18) Uani 1 1 d . . .
H9B H 0.2510 0.2319 0.2983 0.066 Uiso 1 1 calc R . .
C10B C 0.1995(3) 0.1850(6) 0.3418(3) 0.0432(15) Uani 1 1 d . . .
C11B C 0.2552(3) 0.1911(11) 0.4103(4) 0.076(3) Uani 1 1 d . . .
C12B C 0.1900(4) -0.1442(8) 0.4969(4) 0.067(2) Uani 1 1 d . . .
C13B C 0.1166(3) -0.1460(6) 0.4479(3) 0.0527(18) Uani 1 1 d . . .
C14B C 0.0745(4) -0.1794(7) 0.4682(3) 0.062(2) Uani 1 1 d . . .
H14B H 0.0899 -0.2092 0.5111 0.074 Uiso 1 1 calc R . .
C15B C 0.0099(3) -0.1713(7) 0.4282(3) 0.0569(19) Uani 1 1 d . . .
C16B C -0.0362(5) -0.2043(14) 0.4520(4) 0.108(4) Uani 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1A 0.0342(4) 0.0308(4) 0.0469(5) -0.0015(3) 0.0128(3) -0.0003(3)
207

Cu2A 0.0391(4) 0.0328(4) 0.0534(5) 0.0037(4) 0.0176(4) -0.0016(3)

F1A 0.137(4) 0.076(3) 0.077(3) -0.017(2) 0.051(3) 0.017(3)
F2A 0.091(3) 0.119(4) 0.075(3) -0.013(3) 0.050(3) -0.036(3)
F3A 0.081(3) 0.112(4) 0.054(3) -0.026(2) 0.014(2) -0.018(3)
F4A 0.049(3) 0.111(4) 0.099(4) -0.001(3) 0.038(3) -0.003(2)
F5A 0.038(2) 0.125(4) 0.086(3) -0.024(3) 0.006(2) -0.010(2)
F6A 0.064(3) 0.075(3) 0.167(5) 0.022(3) 0.063(3) 0.029(2)
F7A 0.074(3) 0.115(4) 0.074(3) 0.025(3) 0.043(3) -0.002(3)
F8A 0.055(3) 0.161(5) 0.066(3) 0.029(3) 0.018(2) -0.009(3)
F9A 0.150(5) 0.099(4) 0.068(3) -0.017(3) 0.035(3) -0.045(3)
F10A 0.067(3) 0.160(5) 0.105(4) -0.001(3) 0.053(3) -0.028(3)
F11A 0.099(4) 0.199(6) 0.147(5) -0.074(5) 0.079(4) -0.088(4)
F12A 0.049(3) 0.230(7) 0.188(6) 0.123(6) 0.051(4) 0.039(4)
O1A 0.033(2) 0.028(2) 0.040(2) 0.0011(17) 0.0129(18) 0.0019(18)
O2A 0.041(2) 0.028(2) 0.041(2) 0.0063(18) 0.0175(19) 0.0029(18)
O3A 0.107(4) 0.055(3) 0.107(5) 0.020(3) 0.063(4) 0.018(3)
O4A 0.086(4) 0.071(4) 0.098(4) -0.001(3) 0.012(3) 0.008(3)
O5A 0.042(3) 0.053(3) 0.043(3) -0.005(2) 0.011(2) -0.005(2)
O6A 0.037(2) 0.030(2) 0.053(3) -0.0011(18) 0.021(2) 0.0036(18)
O7A 0.052(3) 0.058(3) 0.042(3) 0.011(2) 0.025(2) -0.002(2)
O8A 0.042(3) 0.046(3) 0.064(3) 0.003(2) 0.027(2) -0.008(2)
C1A 0.037(4) 0.036(4) 0.055(4) -0.002(3) 0.016(3) 0.006(3)
C2A 0.086(6) 0.048(5) 0.053(5) -0.010(3) 0.028(4) 0.022(4)
C3A 0.057(5) 0.061(5) 0.078(5) -0.012(4) 0.020(4) 0.019(4)
C4A 0.039(4) 0.035(4) 0.057(4) 0.010(3) 0.016(3) 0.006(3)
C5A 0.074(5) 0.043(4) 0.058(5) -0.004(3) 0.010(4) 0.006(4)
C6A 0.096(6) 0.053(5) 0.099(6) 0.025(4) 0.012(5) 0.022(4)
C7A 0.058(5) 0.067(6) 0.046(4) -0.022(4) -0.004(4) 0.002(4)
C8A 0.047(4) 0.041(4) 0.046(4) -0.004(3) 0.010(3) -0.003(3)
C9A 0.042(4) 0.047(4) 0.046(4) -0.003(3) 0.001(3) -0.005(3)
C10A 0.043(4) 0.034(4) 0.041(4) -0.002(3) 0.004(3) 0.002(3)
C11A 0.040(5) 0.080(6) 0.063(5) 0.006(4) 0.018(4) 0.016(4)
C12A 0.086(7) 0.091(7) 0.069(6) 0.003(5) 0.044(5) -0.017(6)
C13A 0.068(5) 0.038(4) 0.040(4) 0.003(3) 0.021(4) -0.006(3)
C14A 0.054(5) 0.039(4) 0.069(5) 0.005(3) 0.033(4) -0.010(3)
C15A 0.042(4) 0.027(3) 0.081(5) -0.007(3) 0.032(4) -0.009(3)
C16A 0.063(6) 0.095(7) 0.096(7) -0.016(6) 0.056(5) -0.020(5)
Cu1B 0.0413(4) 0.0325(4) 0.0345(4) 0.0026(3) 0.0142(3) -0.0038(3)
Cu2B 0.0414(4) 0.0334(4) 0.0376(4) 0.0054(3) 0.0181(3) -0.0006(3)
F1B 0.074(3) 0.099(3) 0.073(3) 0.040(3) 0.039(2) 0.004(3)
F2B 0.054(3) 0.141(4) 0.073(3) 0.018(3) 0.028(2) -0.019(3)
F3B 0.096(4) 0.113(4) 0.068(3) -0.002(3) 0.053(3) -0.006(3)
F4B 0.108(4) 0.122(4) 0.061(3) 0.019(3) -0.012(3) 0.015(3)
F5B 0.070(3) 0.224(6) 0.073(3) -0.079(4) 0.008(3) -0.020(4)
208

F6B 0.050(3) 0.165(5) 0.097(4) -0.021(3) 0.010(3) -0.042(3)

F7B 0.082(3) 0.157(4) 0.046(2) 0.036(3) 0.023(2) 0.051(3)
F8B 0.085(3) 0.100(4) 0.086(3) -0.014(3) -0.006(3) 0.007(3)
F9B 0.070(3) 0.158(5) 0.062(3) 0.002(3) 0.028(2) 0.042(3)
F10B 0.238(8) 0.310(11) 0.176(7) -0.068(7) 0.154(7) -0.189(9)
F11B 0.323(13) 0.187(8) 0.461(18) 0.026(9) 0.360(14) 0.031(8)
F12B 0.170(7) 0.547(19) 0.120(6) 0.043(8) 0.106(6) -0.073(9)
O1B 0.033(2) 0.031(2) 0.039(2) -0.0006(17) 0.0189(18) -0.0008(18)
O2B 0.036(2) 0.030(2) 0.025(2) -0.0016(16) 0.0039(17) 0.0019(17)
O31B 0.104(7) 0.029(4) 0.102(8) 0.020(4) 0.067(6) 0.004(4)
O32B 0.065(10) 0.027(6) 0.117(14) -0.014(6) 0.073(10) -0.003(6)
O41B 0.081(8) 0.035(5) 0.056(6) 0.004(4) 0.041(5) -0.011(4)
O42B 0.22(2) 0.029(6) 0.118(12) 0.023(6) 0.102(13) 0.053(8)
O5B 0.059(3) 0.055(3) 0.047(3) 0.012(2) 0.029(2) -0.003(2)
O6B 0.044(3) 0.059(3) 0.041(2) -0.009(2) 0.014(2) -0.010(2)
O7B 0.051(3) 0.053(3) 0.040(2) 0.012(2) 0.021(2) 0.011(2)
O8B 0.049(3) 0.067(3) 0.051(3) -0.005(2) 0.028(2) -0.013(2)
C1B 0.025(3) 0.043(4) 0.044(3) -0.002(3) 0.024(3) 0.007(3)
C2B 0.061(6) 0.035(4) 0.131(7) 0.004(4) 0.065(6) 0.000(4)
C3B 0.068(5) 0.052(5) 0.123(7) 0.011(4) 0.052(5) 0.025(4)
C4B 0.057(4) 0.042(4) 0.045(4) -0.009(3) 0.032(3) -0.015(3)
C5B 0.106(6) 0.031(4) 0.044(4) 0.003(3) 0.029(5) -0.005(4)
C6B 0.209(10) 0.084(6) 0.060(5) -0.052(5) 0.070(6) -0.057(6)
C7B 0.035(4) 0.092(7) 0.087(6) 0.008(5) 0.032(4) -0.013(5)
C8B 0.045(4) 0.052(4) 0.046(4) 0.015(3) 0.028(3) 0.000(3)
C9B 0.032(4) 0.053(4) 0.090(6) 0.004(4) 0.036(4) -0.003(3)
C10B 0.032(4) 0.046(4) 0.054(4) -0.009(3) 0.023(3) -0.008(3)
C11B 0.042(5) 0.149(9) 0.048(5) -0.050(5) 0.030(4) -0.030(5)
C12B 0.074(6) 0.063(5) 0.051(5) 0.016(4) 0.020(4) 0.023(4)
C13B 0.080(5) 0.037(4) 0.049(4) -0.005(3) 0.038(4) 0.025(4)
C14B 0.095(6) 0.074(5) 0.023(3) 0.004(3) 0.034(4) 0.018(4)
C15B 0.067(5) 0.070(5) 0.033(4) 0.009(3) 0.023(4) -0.016(4)
C16B 0.111(8) 0.183(11) 0.033(5) -0.010(6) 0.038(5) -0.079(8)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

209

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1A O5A 1.921(4) . ?
Cu1A O1A 1.949(3) . ?
Cu1A O6A 1.953(4) . ?
Cu1A O1A 1.955(4) 2_655 ?
Cu1A O2A 2.388(4) . ?
Cu1A Cu1A 2.9744(17) 2_655 ?
Cu2A O8A 1.935(4) . ?
Cu2A O2A 1.942(4) 2_655 ?
Cu2A O2A 1.942(4) . ?
Cu2A O7A 1.950(4) . ?
Cu2A O1A 2.344(3) . ?
Cu2A Cu2A 2.9649(17) 2_655 ?
F1A C7A 1.344(8) . ?
F2A C7A 1.302(9) . ?
F3A C7A 1.333(7) . ?
F4A C11A 1.332(7) . ?
F5A C11A 1.288(7) . ?
F6A C11A 1.340(8) . ?
F7A C12A 1.348(8) . ?
F8A C12A 1.317(9) . ?
F9A C12A 1.345(9) . ?
F10A C16A 1.301(8) . ?
F11A C16A 1.328(9) . ?
F12A C16A 1.253(9) . ?
O1A C1A 1.447(6) . ?
O1A Cu1A 1.955(4) 2_655 ?
O2A C4A 1.431(6) . ?
O2A Cu2A 1.942(4) 2_655 ?
O3A C2A 1.352(7) . ?
O4A C5A 1.427(8) . ?
O5A C8A 1.270(7) . ?
O6A C10A 1.262(6) . ?
O7A C13A 1.255(7) . ?
O8A C15A 1.289(7) . ?
C1A C2A 1.511(8) . ?
C1A H1A1 0.9900 . ?
C1A H1A2 0.9900 . ?
C2A C3A 1.512(8) . ?
210

C2A H2A 1.0000 . ?

C3A H3A1 0.9800 . ?
C3A H3A2 0.9800 . ?
C3A H3A3 0.9800 . ?
C4A C5A 1.501(8) . ?
C4A H4A1 0.9900 . ?
C4A H4A2 0.9900 . ?
C5A C6A 1.554(9) . ?
C5A H5A 1.0000 . ?
C6A H6A1 0.9800 . ?
C6A H6A2 0.9800 . ?
C6A H6A3 0.9800 . ?
C7A C8A 1.554(9) . ?
C8A C9A 1.387(8) . ?
C9A C10A 1.356(8) . ?
C9A H9A 0.9500 . ?
C10A C11A 1.504(9) . ?
C12A C13A 1.507(9) . ?
C13A C14A 1.388(9) . ?
C14A C15A 1.377(9) . ?
C14A H14A 0.9500 . ?
C15A C16A 1.490(9) . ?
Cu1B O5B 1.937(4) . ?
Cu1B O2B 1.944(4) . ?
Cu1B O6B 1.945(4) . ?
Cu1B O2B 1.963(3) 2 ?
Cu1B O1B 2.346(3) . ?
Cu1B Cu1B 2.9753(18) 2 ?
Cu2B O7B 1.931(4) . ?
Cu2B O8B 1.943(4) . ?
Cu2B O1B 1.955(3) . ?
Cu2B O1B 1.955(3) 2 ?
Cu2B O2B 2.337(3) . ?
Cu2B Cu2B 2.9414(17) 2 ?
F1B C7B 1.319(8) . ?
F2B C7B 1.306(7) . ?
F3B C7B 1.334(8) . ?
F4B C11B 1.315(10) . ?
F5B C11B 1.298(8) . ?
F6B C11B 1.321(8) . ?
F7B C12B 1.325(7) . ?
F8B C12B 1.330(8) . ?
F9B C12B 1.284(8) . ?
F10B C16B 1.231(10) . ?
211

F11B C16B 1.299(14) . ?

F12B C16B 1.266(11) . ?
O1B C1B 1.407(6) . ?
O1B Cu2B 1.955(3) 2 ?
O2B C4B 1.455(6) . ?
O2B Cu1B 1.963(3) 2 ?
O31B C2B 1.339(10) . ?
O31B O32B 1.547(15) . ?
O32B C2B 1.302(13) . ?
O41B C5B 1.385(10) . ?
O41B O42B 1.555(17) . ?
O42B C5B 1.242(15) . ?
O5B C8B 1.279(7) . ?
O6B C10B 1.252(6) . ?
O7B C13B 1.245(7) . ?
O8B C15B 1.239(7) . ?
C1B C2B 1.507(8) . ?
C1B H1B1 0.9900 . ?
C1B H1B2 0.9900 . ?
C2B C3B 1.490(9) . ?
C4B C5B 1.461(8) . ?
C4B H4B1 0.9900 . ?
C4B H4B2 0.9900 . ?
C5B C6B 1.485(9) . ?
C7B C8B 1.500(9) . ?
C8B C9B 1.384(8) . ?
C9B C10B 1.384(8) . ?
C9B H9B 0.9500 . ?
C10B C11B 1.533(9) . ?
C12B C13B 1.578(10) . ?
C13B C14B 1.357(9) . ?
C14B C15B 1.378(9) . ?
C14B H14B 0.9500 . ?
C15B C16B 1.505(10) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O5A Cu1A O1A 94.00(16) . . ?
212

O5A Cu1A O6A 92.47(17) . . ?

O1A Cu1A O6A 170.49(15) . . ?
O5A Cu1A O1A 166.69(16) . 2_655 ?
O1A Cu1A O1A 80.27(16) . 2_655 ?
O6A Cu1A O1A 94.79(16) . 2_655 ?
O5A Cu1A O2A 109.81(15) . . ?
O1A Cu1A O2A 82.71(13) . . ?
O6A Cu1A O2A 88.55(13) . . ?
O1A Cu1A O2A 81.55(13) 2_655 . ?
O5A Cu1A Cu1A 131.59(13) . 2_655 ?
O1A Cu1A Cu1A 40.43(10) . 2_655 ?
O6A Cu1A Cu1A 135.07(12) . 2_655 ?
O1A Cu1A Cu1A 40.29(10) 2_655 2_655 ?
O2A Cu1A Cu1A 84.33(8) . 2_655 ?
O8A Cu2A O2A 94.91(17) . 2_655 ?
O8A Cu2A O2A 172.85(16) . . ?
O2A Cu2A O2A 80.29(16) 2_655 . ?
O8A Cu2A O7A 92.09(18) . . ?
O2A Cu2A O7A 173.00(17) 2_655 . ?
O2A Cu2A O7A 92.72(16) . . ?
O8A Cu2A O1A 100.72(14) . . ?
O2A Cu2A O1A 82.96(13) 2_655 . ?
O2A Cu2A O1A 84.02(13) . . ?
O7A Cu2A O1A 96.05(15) . . ?
O8A Cu2A Cu2A 134.36(14) . 2_655 ?
O2A Cu2A Cu2A 40.24(11) 2_655 2_655 ?
O2A Cu2A Cu2A 40.23(10) . 2_655 ?
O7A Cu2A Cu2A 132.81(13) . 2_655 ?
O1A Cu2A Cu2A 84.50(9) . 2_655 ?
C1A O1A Cu1A 123.7(3) . . ?
C1A O1A Cu1A 118.5(3) . 2_655 ?
Cu1A O1A Cu1A 99.28(16) . 2_655 ?
C1A O1A Cu2A 116.1(3) . . ?
Cu1A O1A Cu2A 96.34(14) . . ?
Cu1A O1A Cu2A 97.83(14) 2_655 . ?
C4A O2A Cu2A 121.8(3) . 2_655 ?
C4A O2A Cu2A 121.4(3) . . ?
Cu2A O2A Cu2A 99.52(16) 2_655 . ?
C4A O2A Cu1A 116.5(3) . . ?
Cu2A O2A Cu1A 96.75(14) 2_655 . ?
Cu2A O2A Cu1A 95.12(14) . . ?
C8A O5A Cu1A 124.4(4) . . ?
C10A O6A Cu1A 125.2(4) . . ?
C13A O7A Cu2A 125.6(4) . . ?
213

C15A O8A Cu2A 125.0(4) . . ?

O1A C1A C2A 111.2(5) . . ?
O1A C1A H1A1 109.4 . . ?
C2A C1A H1A1 109.4 . . ?
O1A C1A H1A2 109.4 . . ?
C2A C1A H1A2 109.4 . . ?
H1A1 C1A H1A2 108.0 . . ?
O3A C2A C3A 113.9(6) . . ?
O3A C2A C1A 110.2(5) . . ?
C3A C2A C1A 111.0(6) . . ?
O3A C2A H2A 107.2 . . ?
C3A C2A H2A 107.2 . . ?
C1A C2A H2A 107.2 . . ?
C2A C3A H3A1 109.5 . . ?
C2A C3A H3A2 109.5 . . ?
H3A1 C3A H3A2 109.5 . . ?
C2A C3A H3A3 109.5 . . ?
H3A1 C3A H3A3 109.5 . . ?
H3A2 C3A H3A3 109.5 . . ?
O2A C4A C5A 110.6(5) . . ?
O2A C4A H4A1 109.5 . . ?
C5A C4A H4A1 109.5 . . ?
O2A C4A H4A2 109.5 . . ?
C5A C4A H4A2 109.5 . . ?
H4A1 C4A H4A2 108.1 . . ?
O4A C5A C4A 108.9(6) . . ?
O4A C5A C6A 108.4(6) . . ?
C4A C5A C6A 112.3(6) . . ?
O4A C5A H5A 109.1 . . ?
C4A C5A H5A 109.1 . . ?
C6A C5A H5A 109.1 . . ?
C5A C6A H6A1 109.5 . . ?
C5A C6A H6A2 109.5 . . ?
H6A1 C6A H6A2 109.5 . . ?
C5A C6A H6A3 109.5 . . ?
H6A1 C6A H6A3 109.5 . . ?
H6A2 C6A H6A3 109.5 . . ?
F2A C7A F3A 108.9(7) . . ?
F2A C7A F1A 109.4(7) . . ?
F3A C7A F1A 104.2(6) . . ?
F2A C7A C8A 114.1(6) . . ?
F3A C7A C8A 111.5(6) . . ?
F1A C7A C8A 108.3(6) . . ?
O5A C8A C9A 127.7(6) . . ?
214

O5A C8A C7A 111.7(6) . . ?

C9A C8A C7A 120.5(6) . . ?
C10A C9A C8A 122.8(6) . . ?
C10A C9A H9A 118.6 . . ?
C8A C9A H9A 118.6 . . ?
O6A C10A C9A 126.9(6) . . ?
O6A C10A C11A 114.9(6) . . ?
C9A C10A C11A 118.1(6) . . ?
F5A C11A F4A 107.5(7) . . ?
F5A C11A F6A 109.2(6) . . ?
F4A C11A F6A 104.1(6) . . ?
F5A C11A C10A 114.6(6) . . ?
F4A C11A C10A 111.7(6) . . ?
F6A C11A C10A 109.2(6) . . ?
F8A C12A F9A 107.6(7) . . ?
F8A C12A F7A 107.1(7) . . ?
F9A C12A F7A 103.8(7) . . ?
F8A C12A C13A 112.8(7) . . ?
F9A C12A C13A 110.9(7) . . ?
F7A C12A C13A 114.0(7) . . ?
O7A C13A C14A 127.6(6) . . ?
O7A C13A C12A 113.4(6) . . ?
C14A C13A C12A 119.0(7) . . ?
C15A C14A C13A 122.0(6) . . ?
C15A C14A H14A 119.0 . . ?
C13A C14A H14A 119.0 . . ?
O8A C15A C14A 127.4(6) . . ?
O8A C15A C16A 112.1(6) . . ?
C14A C15A C16A 120.5(7) . . ?
F12A C16A F10A 109.6(7) . . ?
F12A C16A F11A 104.2(8) . . ?
F10A C16A F11A 104.8(7) . . ?
F12A C16A C15A 113.9(7) . . ?
F10A C16A C15A 113.8(8) . . ?
F11A C16A C15A 109.7(7) . . ?
O5B Cu1B O2B 172.76(16) . . ?
O5B Cu1B O6B 92.26(18) . . ?
O2B Cu1B O6B 93.83(16) . . ?
O5B Cu1B O2B 93.36(17) . 2 ?
O2B Cu1B O2B 80.45(15) . 2 ?
O6B Cu1B O2B 174.15(17) . 2 ?
O5B Cu1B O1B 99.56(15) . . ?
O2B Cu1B O1B 83.49(13) . . ?
O6B Cu1B O1B 97.77(15) . . ?
215

O2B Cu1B O1B 82.91(13) 2 . ?

O5B Cu1B Cu1B 132.75(13) . 2 ?
O2B Cu1B Cu1B 40.62(10) . 2 ?
O6B Cu1B Cu1B 134.03(14) . 2 ?
O2B Cu1B Cu1B 40.15(11) 2 2 ?
O1B Cu1B Cu1B 85.04(8) . 2 ?
O7B Cu2B O8B 92.46(18) . . ?
O7B Cu2B O1B 92.09(16) . . ?
O8B Cu2B O1B 171.49(16) . . ?
O7B Cu2B O1B 174.27(16) . 2 ?
O8B Cu2B O1B 93.23(16) . 2 ?
O1B Cu2B O1B 82.18(15) . 2 ?
O7B Cu2B O2B 96.12(14) . . ?
O8B Cu2B O2B 103.16(15) . . ?
O1B Cu2B O2B 83.48(13) . . ?
O1B Cu2B O2B 83.30(13) 2 . ?
O7B Cu2B Cu2B 133.06(13) . 2 ?
O8B Cu2B Cu2B 133.17(13) . 2 ?
O1B Cu2B Cu2B 41.22(10) . 2 ?
O1B Cu2B Cu2B 41.22(10) 2 2 ?
O2B Cu2B Cu2B 84.86(8) . 2 ?
C1B O1B Cu2B 120.6(3) . . ?
C1B O1B Cu2B 122.5(3) . 2 ?
Cu2B O1B Cu2B 97.56(15) . 2 ?
C1B O1B Cu1B 118.4(3) . . ?
Cu2B O1B Cu1B 95.60(14) . . ?
Cu2B O1B Cu1B 96.39(14) 2 . ?
C4B O2B Cu1B 120.3(3) . . ?
C4B O2B Cu1B 121.1(3) . 2 ?
Cu1B O2B Cu1B 99.22(15) . 2 ?
C4B O2B Cu2B 118.2(3) . . ?
Cu1B O2B Cu2B 96.21(14) . . ?
Cu1B O2B Cu2B 96.47(13) 2 . ?
C2B O31B O32B 53.0(6) . . ?
C2B O32B O31B 55.3(7) . . ?
C5B O41B O42B 49.6(6) . . ?
C5B O42B O41B 58.1(9) . . ?
C8B O5B Cu1B 126.6(4) . . ?
C10B O6B Cu1B 124.5(4) . . ?
C13B O7B Cu2B 123.8(4) . . ?
C15B O8B Cu2B 123.9(4) . . ?
O1B C1B C2B 113.9(5) . . ?
O1B C1B H1B1 108.8 . . ?
C2B C1B H1B1 108.8 . . ?
216

O1B C1B H1B2 108.8 . . ?

C2B C1B H1B2 108.7 . . ?
H1B1 C1B H1B2 107.7 . . ?
O32B C2B O31B 71.7(7) . . ?
O32B C2B C3B 121.3(8) . . ?
O31B C2B C3B 115.9(7) . . ?
O32B C2B C1B 112.6(7) . . ?
O31B C2B C1B 110.5(6) . . ?
C3B C2B C1B 116.6(6) . . ?
O2B C4B C5B 113.1(5) . . ?
O2B C4B H4B1 109.0 . . ?
C5B C4B H4B1 108.9 . . ?
O2B C4B H4B2 109.0 . . ?
C5B C4B H4B2 109.0 . . ?
H4B1 C4B H4B2 107.8 . . ?
O42B C5B O41B 72.4(8) . . ?
O42B C5B C4B 112.4(8) . . ?
O41B C5B C4B 111.4(6) . . ?
O42B C5B C6B 123.6(9) . . ?
O41B C5B C6B 116.9(7) . . ?
C4B C5B C6B 113.5(6) . . ?
F2B C7B F1B 108.2(6) . . ?
F2B C7B F3B 108.7(7) . . ?
F1B C7B F3B 108.5(7) . . ?
F2B C7B C8B 110.9(7) . . ?
F1B C7B C8B 109.9(6) . . ?
F3B C7B C8B 110.5(6) . . ?
O5B C8B C9B 124.4(6) . . ?
O5B C8B C7B 112.4(6) . . ?
C9B C8B C7B 123.2(6) . . ?
C8B C9B C10B 124.0(6) . . ?
C8B C9B H9B 118.0 . . ?
C10B C9B H9B 118.0 . . ?
O6B C10B C9B 127.6(6) . . ?
O6B C10B C11B 112.2(6) . . ?
C9B C10B C11B 120.0(6) . . ?
F5B C11B F4B 109.5(7) . . ?
F5B C11B F6B 103.9(7) . . ?
F4B C11B F6B 110.1(7) . . ?
F5B C11B C10B 110.1(6) . . ?
F4B C11B C10B 112.2(7) . . ?
F6B C11B C10B 110.8(7) . . ?
F9B C12B F7B 108.2(6) . . ?
F9B C12B F8B 109.2(7) . . ?
217

F7B C12B F8B 106.6(6) . . ?

F9B C12B C13B 112.9(6) . . ?
F7B C12B C13B 111.1(7) . . ?
F8B C12B C13B 108.6(6) . . ?
O7B C13B C14B 129.0(7) . . ?
O7B C13B C12B 110.8(6) . . ?
C14B C13B C12B 120.2(6) . . ?
C13B C14B C15B 121.8(6) . . ?
C13B C14B H14B 119.1 . . ?
C15B C14B H14B 119.1 . . ?
O8B C15B C14B 128.0(6) . . ?
O8B C15B C16B 110.8(7) . . ?
C14B C15B C16B 121.2(7) . . ?
F10B C16B F12B 102.0(11) . . ?
F10B C16B F11B 108.9(11) . . ?
F12B C16B F11B 105.9(10) . . ?
F10B C16B C15B 113.9(9) . . ?
F12B C16B C15B 111.6(9) . . ?
F11B C16B C15B 113.6(10) . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O5A Cu1A O1A C1A -27.1(4) . . . . ?
O6A Cu1A O1A C1A -159.9(9) . . . . ?
O1A Cu1A O1A C1A 140.8(3) 2_655 . . . ?
O2A Cu1A O1A C1A -136.6(4) . . . . ?
Cu1A Cu1A O1A C1A 133.6(4) 2_655 . . . ?
O5A Cu1A O1A Cu1A -160.71(16) . . . 2_655 ?
O6A Cu1A O1A Cu1A 66.5(10) . . . 2_655 ?
O1A Cu1A O1A Cu1A 7.2(2) 2_655 . . 2_655 ?
O2A Cu1A O1A Cu1A 89.81(15) . . . 2_655 ?
O5A Cu1A O1A Cu2A 100.26(15) . . . . ?
O6A Cu1A O1A Cu2A -32.5(10) . . . . ?
O1A Cu1A O1A Cu2A -91.84(12) 2_655 . . . ?
O2A Cu1A O1A Cu2A -9.22(12) . . . . ?
218

Cu1A Cu1A O1A Cu2A -99.03(17) 2_655 . . . ?

O8A Cu2A O1A C1A -41.5(4) . . . . ?
O2A Cu2A O1A C1A -135.2(3) 2_655 . . . ?
O2A Cu2A O1A C1A 143.9(3) . . . . ?
O7A Cu2A O1A C1A 51.8(3) . . . . ?
Cu2A Cu2A O1A C1A -175.7(3) 2_655 . . . ?
O8A Cu2A O1A Cu1A -174.07(16) . . . . ?
O2A Cu2A O1A Cu1A 92.24(16) 2_655 . . . ?
O2A Cu2A O1A Cu1A 11.33(15) . . . . ?
O7A Cu2A O1A Cu1A -80.78(17) . . . . ?
Cu2A Cu2A O1A Cu1A 51.77(11) 2_655 . . . ?
O8A Cu2A O1A Cu1A 85.61(18) . . . 2_655 ?
O2A Cu2A O1A Cu1A -8.07(15) 2_655 . . 2_655 ?
O2A Cu2A O1A Cu1A -88.98(16) . . . 2_655 ?
O7A Cu2A O1A Cu1A 178.91(16) . . . 2_655 ?
Cu2A Cu2A O1A Cu1A -48.54(11) 2_655 . . 2_655 ?
O8A Cu2A O2A C4A 93.4(14) . . . . ?
O2A Cu2A O2A C4A 141.5(3) 2_655 . . . ?
O7A Cu2A O2A C4A -38.9(4) . . . . ?
O1A Cu2A O2A C4A -134.7(4) . . . . ?
Cu2A Cu2A O2A C4A 136.8(4) 2_655 . . . ?
O8A Cu2A O2A Cu2A -43.4(14) . . . 2_655 ?
O2A Cu2A O2A Cu2A 4.7(2) 2_655 . . 2_655 ?
O7A Cu2A O2A Cu2A -175.66(16) . . . 2_655 ?
O1A Cu2A O2A Cu2A 88.54(15) . . . 2_655 ?
O8A Cu2A O2A Cu1A -141.2(13) . . . . ?
O2A Cu2A O2A Cu1A -93.06(12) 2_655 . . . ?
O7A Cu2A O2A Cu1A 86.60(15) . . . . ?
O1A Cu2A O2A Cu1A -9.21(12) . . . . ?
Cu2A Cu2A O2A Cu1A -97.74(16) 2_655 . . . ?
O5A Cu1A O2A C4A 48.5(4) . . . . ?
O1A Cu1A O2A C4A 140.2(4) . . . . ?
O6A Cu1A O2A C4A -43.6(4) . . . . ?
O1A Cu1A O2A C4A -138.7(4) 2_655 . . . ?
Cu1A Cu1A O2A C4A -179.2(4) 2_655 . . . ?
O5A Cu1A O2A Cu2A 179.23(16) . . . 2_655 ?
O1A Cu1A O2A Cu2A -89.12(16) . . . 2_655 ?
O6A Cu1A O2A Cu2A 87.12(16) . . . 2_655 ?
O1A Cu1A O2A Cu2A -7.93(14) 2_655 . . 2_655 ?
Cu1A Cu1A O2A Cu2A -48.45(12) 2_655 . . 2_655 ?
O5A Cu1A O2A Cu2A -80.52(18) . . . . ?
O1A Cu1A O2A Cu2A 11.12(15) . . . . ?
O6A Cu1A O2A Cu2A -172.63(16) . . . . ?
O1A Cu1A O2A Cu2A 92.31(15) 2_655 . . . ?
219

Cu1A Cu1A O2A Cu2A 51.80(11) 2_655 . . . ?

O1A Cu1A O5A C8A -176.4(5) . . . . ?
O6A Cu1A O5A C8A -3.3(5) . . . . ?
O1A Cu1A O5A C8A 119.7(7) 2_655 . . . ?
O2A Cu1A O5A C8A -92.7(5) . . . . ?
Cu1A Cu1A O5A C8A 167.0(4) 2_655 . . . ?
O5A Cu1A O6A C10A -2.3(4) . . . . ?
O1A Cu1A O6A C10A 130.6(9) . . . . ?
O1A Cu1A O6A C10A -171.1(4) 2_655 . . . ?
O2A Cu1A O6A C10A 107.5(4) . . . . ?
Cu1A Cu1A O6A C10A -172.0(4) 2_655 . . . ?
O8A Cu2A O7A C13A -0.4(5) . . . . ?
O2A Cu2A O7A C13A 177.1(11) 2_655 . . . ?
O2A Cu2A O7A C13A 174.3(5) . . . . ?
O1A Cu2A O7A C13A -101.4(5) . . . . ?
Cu2A Cu2A O7A C13A 170.5(4) 2_655 . . . ?
O2A Cu2A O8A C15A -175.3(4) 2_655 . . . ?
O2A Cu2A O8A C15A -127.9(13) . . . . ?
O7A Cu2A O8A C15A 4.3(5) . . . . ?
O1A Cu2A O8A C15A 100.9(4) . . . . ?
Cu2A Cu2A O8A C15A -166.3(4) 2_655 . . . ?
Cu1A O1A C1A C2A -61.6(6) . . . . ?
Cu1A O1A C1A C2A 64.0(5) 2_655 . . . ?
Cu2A O1A C1A C2A -179.9(4) . . . . ?
O1A C1A C2A O3A -38.7(7) . . . . ?
O1A C1A C2A C3A -165.8(5) . . . . ?
Cu2A O2A C4A C5A 73.0(6) 2_655 . . . ?
Cu2A O2A C4A C5A -54.4(6) . . . . ?
Cu1A O2A C4A C5A -169.4(4) . . . . ?
O2A C4A C5A O4A -51.2(7) . . . . ?
O2A C4A C5A C6A -171.3(6) . . . . ?
Cu1A O5A C8A C9A 7.7(9) . . . . ?
Cu1A O5A C8A C7A -175.9(4) . . . . ?
F2A C7A C8A O5A -47.6(8) . . . . ?
F3A C7A C8A O5A -171.4(6) . . . . ?
F1A C7A C8A O5A 74.5(7) . . . . ?
F2A C7A C8A C9A 129.1(7) . . . . ?
F3A C7A C8A C9A 5.3(10) . . . . ?
F1A C7A C8A C9A -108.8(7) . . . . ?
O5A C8A C9A C10A -6.0(10) . . . . ?
C7A C8A C9A C10A 177.9(6) . . . . ?
Cu1A O6A C10A C9A 4.4(9) . . . . ?
Cu1A O6A C10A C11A -173.6(4) . . . . ?
C8A C9A C10A O6A -0.8(10) . . . . ?
220

C8A C9A C10A C11A 177.2(6) . . . . ?

O6A C10A C11A F5A -160.6(6) . . . . ?
C9A C10A C11A F5A 21.2(10) . . . . ?
O6A C10A C11A F4A -38.0(9) . . . . ?
C9A C10A C11A F4A 143.7(6) . . . . ?
O6A C10A C11A F6A 76.5(7) . . . . ?
C9A C10A C11A F6A -101.7(7) . . . . ?
Cu2A O7A C13A C14A -3.8(9) . . . . ?
Cu2A O7A C13A C12A 176.1(5) . . . . ?
F8A C12A C13A O7A 36.0(9) . . . . ?
F9A C12A C13A O7A -84.8(8) . . . . ?
F7A C12A C13A O7A 158.4(6) . . . . ?
F8A C12A C13A C14A -144.2(6) . . . . ?
F9A C12A C13A C14A 95.0(8) . . . . ?
F7A C12A C13A C14A -21.7(10) . . . . ?
O7A C13A C14A C15A 4.7(10) . . . . ?
C12A C13A C14A C15A -175.1(6) . . . . ?
Cu2A O8A C15A C14A -4.8(9) . . . . ?
Cu2A O8A C15A C16A 177.5(5) . . . . ?
C13A C14A C15A O8A 0.0(10) . . . . ?
C13A C14A C15A C16A 177.6(7) . . . . ?
O8A C15A C16A F12A 58.0(9) . . . . ?
C14A C15A C16A F12A -119.9(8) . . . . ?
O8A C15A C16A F10A -175.5(6) . . . . ?
C14A C15A C16A F10A 6.7(11) . . . . ?
O8A C15A C16A F11A -58.4(9) . . . . ?
C14A C15A C16A F11A 123.7(7) . . . . ?
O7B Cu2B O1B C1B 39.4(4) . . . . ?
O8B Cu2B O1B C1B -82.8(12) . . . . ?
O1B Cu2B O1B C1B -140.5(3) 2 . . . ?
O2B Cu2B O1B C1B 135.4(3) . . . . ?
Cu2B Cu2B O1B C1B -135.0(4) 2 . . . ?
O7B Cu2B O1B Cu2B 174.44(16) . . . 2 ?
O8B Cu2B O1B Cu2B 52.2(12) . . . 2 ?
O1B Cu2B O1B Cu2B -5.5(2) 2 . . 2 ?
O2B Cu2B O1B Cu2B -89.63(14) . . . 2 ?
O7B Cu2B O1B Cu1B -88.33(15) . . . . ?
O8B Cu2B O1B Cu1B 149.4(11) . . . . ?
O1B Cu2B O1B Cu1B 91.70(12) 2 . . . ?
O2B Cu2B O1B Cu1B 7.60(12) . . . . ?
Cu2B Cu2B O1B Cu1B 97.23(16) 2 . . . ?
O5B Cu1B O1B C1B 48.2(4) . . . . ?
O2B Cu1B O1B C1B -138.5(3) . . . . ?
O6B Cu1B O1B C1B -45.5(4) . . . . ?
221

O2B Cu1B O1B C1B 140.4(3) 2 . . . ?

Cu1B Cu1B O1B C1B -179.3(3) 2 . . . ?
O5B Cu1B O1B Cu2B 177.48(16) . . . . ?
O2B Cu1B O1B Cu2B -9.15(14) . . . . ?
O6B Cu1B O1B Cu2B 83.85(17) . . . . ?
O2B Cu1B O1B Cu2B -90.29(16) 2 . . . ?
Cu1B Cu1B O1B Cu2B -49.95(11) 2 . . . ?
O5B Cu1B O1B Cu2B -84.24(17) . . . 2 ?
O2B Cu1B O1B Cu2B 89.13(15) . . . 2 ?
O6B Cu1B O1B Cu2B -177.87(16) . . . 2 ?
O2B Cu1B O1B Cu2B 7.99(14) 2 . . 2 ?
Cu1B Cu1B O1B Cu2B 48.32(11) 2 . . 2 ?
O5B Cu1B O2B C4B -109.1(13) . . . . ?
O6B Cu1B O2B C4B 38.1(4) . . . . ?
O2B Cu1B O2B C4B -140.6(3) 2 . . . ?
O1B Cu1B O2B C4B 135.5(4) . . . . ?
Cu1B Cu1B O2B C4B -134.5(4) 2 . . . ?
O5B Cu1B O2B Cu1B 25.4(13) . . . 2 ?
O6B Cu1B O2B Cu1B 172.64(16) . . . 2 ?
O2B Cu1B O2B Cu1B -6.1(2) 2 . . 2 ?
O1B Cu1B O2B Cu1B -89.96(14) . . . 2 ?
O5B Cu1B O2B Cu2B 123.0(12) . . . . ?
O6B Cu1B O2B Cu2B -89.75(15) . . . . ?
O2B Cu1B O2B Cu2B 91.52(11) 2 . . . ?
O1B Cu1B O2B Cu2B 7.65(12) . . . . ?
Cu1B Cu1B O2B Cu2B 97.62(15) 2 . . . ?
O7B Cu2B O2B C4B -47.2(4) . . . . ?
O8B Cu2B O2B C4B 46.8(4) . . . . ?
O1B Cu2B O2B C4B -138.6(4) . . . . ?
O1B Cu2B O2B C4B 138.6(4) 2 . . . ?
Cu2B Cu2B O2B C4B 180.0(3) 2 . . . ?
O7B Cu2B O2B Cu1B 82.22(16) . . . . ?
O8B Cu2B O2B Cu1B 176.20(15) . . . . ?
O1B Cu2B O2B Cu1B -9.19(14) . . . . ?
O1B Cu2B O2B Cu1B -92.04(15) 2 . . . ?
Cu2B Cu2B O2B Cu1B -50.61(11) 2 . . . ?
O7B Cu2B O2B Cu1B -177.72(16) . . . 2 ?
O8B Cu2B O2B Cu1B -83.75(18) . . . 2 ?
O1B Cu2B O2B Cu1B 90.86(16) . . . 2 ?
O1B Cu2B O2B Cu1B 8.02(14) 2 . . 2 ?
Cu2B Cu2B O2B Cu1B 49.44(11) 2 . . 2 ?
O2B Cu1B O5B C8B 140.3(12) . . . . ?
O6B Cu1B O5B C8B -6.9(5) . . . . ?
O2B Cu1B O5B C8B 171.4(5) 2 . . . ?
222

O1B Cu1B O5B C8B -105.2(5) . . . . ?

Cu1B Cu1B O5B C8B 162.7(4) 2 . . . ?
O5B Cu1B O6B C10B 8.4(5) . . . . ?
O2B Cu1B O6B C10B -167.6(5) . . . . ?
O2B Cu1B O6B C10B -155.3(14) 2 . . . ?
O1B Cu1B O6B C10B 108.4(5) . . . . ?
Cu1B Cu1B O6B C10B -161.0(4) 2 . . . ?
O8B Cu2B O7B C13B 7.9(5) . . . . ?
O1B Cu2B O7B C13B -164.9(4) . . . . ?
O1B Cu2B O7B C13B -164.7(14) 2 . . . ?
O2B Cu2B O7B C13B 111.4(4) . . . . ?
Cu2B Cu2B O7B C13B -159.9(4) 2 . . . ?
O7B Cu2B O8B C15B -10.6(5) . . . . ?
O1B Cu2B O8B C15B 111.6(11) . . . . ?
O1B Cu2B O8B C15B 168.6(5) 2 . . . ?
O2B Cu2B O8B C15B -107.5(5) . . . . ?
Cu2B Cu2B O8B C15B 157.1(4) 2 . . . ?
Cu2B O1B C1B C2B 63.9(6) . . . . ?
Cu2B O1B C1B C2B -60.0(6) 2 . . . ?
Cu1B O1B C1B C2B -179.6(5) . . . . ?
O31B O32B C2B C3B 109.7(9) . . . . ?
O31B O32B C2B C1B -105.1(7) . . . . ?
O32B O31B C2B C3B -116.6(9) . . . . ?
O32B O31B C2B C1B 108.0(8) . . . . ?
O1B C1B C2B O32B 34.9(10) . . . . ?
O1B C1B C2B O31B -43.1(10) . . . . ?
O1B C1B C2B C3B -178.1(6) . . . . ?
Cu1B O2B C4B C5B 61.1(6) . . . . ?
Cu1B O2B C4B C5B -63.6(6) 2 . . . ?
Cu2B O2B C4B C5B 178.2(5) . . . . ?
O41B O42B C5B C4B -106.4(8) . . . . ?
O41B O42B C5B C6B 111.1(10) . . . . ?
O42B O41B C5B C4B 107.8(8) . . . . ?
O42B O41B C5B C6B -119.4(11) . . . . ?
O2B C4B C5B O42B 40.1(12) . . . . ?
O2B C4B C5B O41B -38.9(9) . . . . ?
O2B C4B C5B C6B -173.4(7) . . . . ?
Cu1B O5B C8B C9B 2.4(9) . . . . ?
Cu1B O5B C8B C7B -177.2(5) . . . . ?
F2B C7B C8B O5B 178.8(6) . . . . ?
F1B C7B C8B O5B 59.1(8) . . . . ?
F3B C7B C8B O5B -60.6(8) . . . . ?
F2B C7B C8B C9B -0.8(10) . . . . ?
F1B C7B C8B C9B -120.5(7) . . . . ?
223

F3B C7B C8B C9B 119.8(7) . . . . ?

O5B C8B C9B C10B 3.6(10) . . . . ?
C7B C8B C9B C10B -176.8(7) . . . . ?
Cu1B O6B C10B C9B -5.8(9) . . . . ?
Cu1B O6B C10B C11B 178.2(5) . . . . ?
C8B C9B C10B O6B -1.7(11) . . . . ?
C8B C9B C10B C11B 173.9(7) . . . . ?
O6B C10B C11B F5B -49.5(10) . . . . ?
C9B C10B C11B F5B 134.2(7) . . . . ?
O6B C10B C11B F4B 72.8(7) . . . . ?
C9B C10B C11B F4B -103.5(8) . . . . ?
O6B C10B C11B F6B -163.8(6) . . . . ?
C9B C10B C11B F6B 19.9(10) . . . . ?
Cu2B O7B C13B C14B -2.4(9) . . . . ?
Cu2B O7B C13B C12B 179.1(4) . . . . ?
F9B C12B C13B O7B -37.1(8) . . . . ?
F7B C12B C13B O7B -158.9(6) . . . . ?
F8B C12B C13B O7B 84.2(7) . . . . ?
F9B C12B C13B C14B 144.2(7) . . . . ?
F7B C12B C13B C14B 22.4(9) . . . . ?
F8B C12B C13B C14B -94.5(7) . . . . ?
O7B C13B C14B C15B -3.9(11) . . . . ?
C12B C13B C14B C15B 174.5(6) . . . . ?
Cu2B O8B C15B C14B 8.3(10) . . . . ?
Cu2B O8B C15B C16B -173.1(6) . . . . ?
C13B C14B C15B O8B 0.5(12) . . . . ?
C13B C14B C15B C16B -177.9(8) . . . . ?
O8B C15B C16B F10B 60.0(14) . . . . ?
C14B C15B C16B F10B -121.3(10) . . . . ?
O8B C15B C16B F12B 174.9(11) . . . . ?
C14B C15B C16B F12B -6.4(16) . . . . ?
O8B C15B C16B F11B -65.4(11) . . . . ?
C14B C15B C16B F11B 113.3(11) . . . . ?
_diffrn_measured_fraction_theta_max 0.767
_diffrn_reflns_theta_full
32.0
_diffrn_measured_fraction_theta_full 0.767
_refine_diff_density_max 1.01
_refine_diff_density_min -0.68
_refine_diff_density_rms 0.105
# END OF CIF

224

Table A-10. CIF File For [CuN(t-Bu)(SiMe3)]4

_audit_creation_method
SHELXL-97
_chemical_name_systematic
;
tetrakis(mu-(t-butyl)(trimethylsilyl)amido)tetracopper(I)
;
_chemical_name_common
?
_chemical_melting_point
?
_chemical_formula_moiety
'C28 H72 Cu4 N4 Si4'
_chemical_formula_sum
'C28 H72 Cu4 N4 Si4'
_chemical_formula_weight
831.42
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Si' 'Si' 0.0817 0.0704
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'Cu' 'Cu' 0.3201 1.2651
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_space_group_name_H-M 'P 2/n
_symmetry_cell_setting 'Monoclinic'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y, -z+1/2'
'-x, -y, -z'
'x-1/2, -y, z-1/2'
_cell_length_a
_cell_length_b
_cell_length_c
_cell_angle_alpha

8.852(2)
13.177(3)
17.356(3)
90
225

'

_cell_angle_beta
90.541(10)
_cell_angle_gamma
90
_cell_volume
2024.5(7)
_cell_formula_units_Z
2
_cell_measurement_temperature 120
_cell_measurement_reflns_used 5833
_cell_measurement_theta_min
2.5
_cell_measurement_theta_max
32.0
_exptl_crystal_description
needle
_exptl_crystal_colour
colorless
_exptl_crystal_size_max
0.48
_exptl_crystal_size_mid
0.20
_exptl_crystal_size_min
0.18
_exptl_crystal_density_meas
?
_exptl_crystal_density_diffrn 1.364
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000
880
_exptl_absorpt_coefficient_mu 2.213
_exptl_absorpt_correction_type 'multi-scan'
_exptl_absorpt_correction_T_min 0.416
_exptl_absorpt_correction_T_max 0.691
_exptl_absorpt_process_details 'HKL Scalepack (Otwinowski & Minor 1997)'
_exptl_special_details
;
?
;
_diffrn_ambient_temperature
120
_diffrn_radiation_wavelength
0.71073
_diffrn_radiation_type
MoK\a
_diffrn_radiation_source
'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device 'KappaCCD (with Oxford Cryostream)'
_diffrn_measurement_method
' \w scans with \k offsets'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number
0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time ?
_diffrn_standards_decay_%
<2
_diffrn_reflns_number
25016
_diffrn_reflns_av_R_equivalents 0.042
_diffrn_reflns_av_sigmaI/netI 0.0468
226

_diffrn_reflns_limit_h_min -13
_diffrn_reflns_limit_h_max 13
_diffrn_reflns_limit_k_min -19
_diffrn_reflns_limit_k_max 15
_diffrn_reflns_limit_l_min -25
_diffrn_reflns_limit_l_max 25
_diffrn_reflns_theta_min
2.8
_diffrn_reflns_theta_max
32.0
_reflns_number_total
7008
_reflns_number_gt
4403
_reflns_threshold_expression
I>2\s(I)
_computing_data_collection
?
_computing_cell_refinement
?
_computing_data_reduction
?
_computing_structure_solution ?
_computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics ?
_computing_publication_material ?
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full
_refine_ls_weighting_scheme
calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0994P)^2^+2.9908P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary
direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment noref
_refine_ls_extinction_method
SHELXL
_refine_ls_extinction_coef
0.0130(15)
_refine_ls_extinction_expression
'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^'
227

_refine_ls_number_reflns
7008
_refine_ls_number_parameters
183
_refine_ls_number_restraints
0
_refine_ls_R_factor_all
0.095
_refine_ls_R_factor_gt
0.056
_refine_ls_wR_factor_ref
0.195
_refine_ls_wR_factor_gt
0.167
_refine_ls_goodness_of_fit_ref 0.996
_refine_ls_restrained_S_all
0.996
_refine_ls_shift/su_max
0.001
_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.30317(4) 0.35107(3) 0.17670(2) 0.02676(14) Uani 1 1 d . . .
Cu2 Cu 0.30321(5) 0.14569(3) 0.17682(2) 0.02952(15) Uani 1 1 d . . .
Si1C Si 0.5339(2) 0.25549(14) 0.08463(12) 0.0247(6) Uani 0.204(6) 1 d P . .
C1SI C 0.5339(2) 0.25549(14) 0.08463(12) 0.0247(6) Uani 0.796(6) 1 d P . .
Si2C Si 0.23930(12) 0.23771(8) 0.02400(6) 0.0277(3) Uani 0.796(6) 1 d P . .
C2SI C 0.23930(12) 0.23771(8) 0.02400(6) 0.0277(3) Uani 0.204(6) 1 d P . .
Si3C Si 0.10772(16) 0.52125(10) 0.21334(8) 0.0306(3) Uani 0.50 1 d P . .
C3SI C 0.10772(16) 0.52125(10) 0.21334(8) 0.0306(3) Uani 0.50 1 d P . .
Si4C Si 0.09897(14) -0.02563(9) 0.22231(7) 0.0238(3) Uani 0.50 1 d P . .
C4SI C 0.09897(14) -0.02563(9) 0.22231(7) 0.0238(3) Uani 0.50 1 d P . .
N1 N 0.3591(3) 0.24891(17) 0.10158(15) 0.0244(5) Uani 1 1 d . . .
N2 N 0.2500 0.4561(3) 0.2500 0.0287(8) Uani 1 2 d S . .
N3 N 0.2500 0.0397(3) 0.2500 0.0248(7) Uani 1 2 d S . .
C1 C 0.6224(4) 0.2256(3) 0.1632(2) 0.0399(8) Uani 1 1 d . . .
H1A H 0.7277 0.2454 0.1590 0.060 Uiso 1 1 d . . .
H1B H 0.6160 0.1512 0.1704 0.060 Uiso 1 1 d . . .
H1C H 0.5749 0.2595 0.2064 0.060 Uiso 1 1 d . . .
C2 C 0.5852(5) 0.1761(4) 0.0231(3) 0.0517(10) Uani 1 1 d . . .
228

H2A H 0.5408 0.1927 -0.0275 0.078 Uiso 1 1 d . . .

H2B H 0.5517 0.1069 0.0375 0.078 Uiso 1 1 d . . .
H2C H 0.6959 0.1755 0.0188 0.078 Uiso 1 1 d . . .
C3 C 0.5824(4) 0.3639(3) 0.0619(2) 0.0466(9) Uani 1 1 d . . .
H3A H 0.5339 0.3824 0.0120 0.070 Uiso 1 1 d . . .
H3B H 0.6931 0.3666 0.0549 0.070 Uiso 1 1 d . . .
H3C H 0.5531 0.4128 0.1008 0.070 Uiso 1 1 d . . .
C4 C 0.0506(5) 0.2742(3) 0.0524(2) 0.0420(8) Uani 1 1 d . . .
H4A H 0.0273 0.2444 0.1026 0.063 Uiso 1 1 d . . .
H4B H -0.0229 0.2499 0.0139 0.063 Uiso 1 1 d . . .
H4C H 0.0439 0.3485 0.0559 0.063 Uiso 1 1 d . . .
C5 C 0.2293(5) 0.1085(4) -0.0118(2) 0.0513(10) Uani 1 1 d . . .
H5A H 0.3274 0.0907 -0.0338 0.077 Uiso 1 1 d . . .
H5B H 0.1509 0.1049 -0.0515 0.077 Uiso 1 1 d . . .
H5C H 0.2060 0.0634 0.0307 0.077 Uiso 1 1 d . . .
C6 C 0.2798(5) 0.3186(4) -0.0576(3) 0.0580(11) Uani 1 1 d . . .
H6A H 0.2866 0.3891 -0.0400 0.087 Uiso 1 1 d . . .
H6B H 0.1972 0.3123 -0.0954 0.087 Uiso 1 1 d . . .
H6C H 0.3745 0.2977 -0.0805 0.087 Uiso 1 1 d . . .
C7 C 0.0516(6) 0.6187(4) 0.2685(3) 0.0689(14) Uani 1 1 d . . .
H7A H 0.0270 0.5950 0.3201 0.103 Uiso 1 1 d . . .
H7B H -0.0366 0.6518 0.2451 0.103 Uiso 1 1 d . . .
H7C H 0.1345 0.6693 0.2725 0.103 Uiso 1 1 d . . .
C8 C -0.0459(5) 0.4425(3) 0.2088(2) 0.0466(9) Uani 1 1 d . . .
H8A H -0.0184 0.3785 0.1855 0.070 Uiso 1 1 d . . .
H8B H -0.1268 0.4753 0.1781 0.070 Uiso 1 1 d . . .
H8C H -0.0844 0.4307 0.2613 0.070 Uiso 1 1 d . . .
C9 C 0.1417(6) 0.5628(4) 0.1243(3) 0.0654(13) Uani 1 1 d . . .
H9A H 0.2280 0.6086 0.1264 0.098 Uiso 1 1 d . . .
H9B H 0.0524 0.5978 0.1051 0.098 Uiso 1 1 d . . .
H9C H 0.1644 0.5041 0.0921 0.098 Uiso 1 1 d . . .
C10 C -0.0196(5) 0.0556(3) 0.1755(2) 0.0434(8) Uani 1 1 d . . .
H10A H 0.0204 0.0690 0.1241 0.065 Uiso 1 1 d . . .
H10B H -0.0271 0.1179 0.2047 0.065 Uiso 1 1 d . . .
H10C H -0.1192 0.0232 0.1706 0.065 Uiso 1 1 d . . .
C11 C 0.0020(5) -0.0697(3) 0.3008(2) 0.0488(10) Uani 1 1 d . . .
H11A H -0.0958 -0.0961 0.2834 0.073 Uiso 1 1 d . . .
H11B H -0.0123 -0.0142 0.3369 0.073 Uiso 1 1 d . . .
H11C H 0.0608 -0.1241 0.3250 0.073 Uiso 1 1 d . . .
C12 C 0.1333(5) -0.1194 0.1642(3) 0.0638(14) Uani 1 1 d . . .
H12A H 0.1863 -0.0945 0.1196 0.096 Uiso 1 1 d . . .
H12B H 0.0384 -0.1515 0.1496 0.096 Uiso 1 1 d . . .
H12C H 0.1973 -0.1691 0.1922 0.096 Uiso 1 1 d . . .

229

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0316(2) 0.0224(2) 0.0264(2) -0.00085(13) 0.00744(15) 0.00223(13)
Cu2 0.0357(2) 0.0263(2) 0.0266(2) 0.00157(14) 0.00208(16) 0.00211(14)
Si1C 0.0215(9) 0.0297(11) 0.0231(10) -0.0034(7) 0.0037(7) 0.0024(7)
C1SI 0.0215(9) 0.0297(11) 0.0231(10) -0.0034(7) 0.0037(7) 0.0024(7)
Si2C 0.0289(5) 0.0349(6) 0.0192(5) 0.0016(4) -0.0004(3) 0.0022(4)
C2SI 0.0289(5) 0.0349(6) 0.0192(5) 0.0016(4) -0.0004(3) 0.0022(4)
Si3C 0.0325(7) 0.0237(6) 0.0359(7) 0.0054(5) 0.0110(5) 0.0082(5)
C3SI 0.0325(7) 0.0237(6) 0.0359(7) 0.0054(5) 0.0110(5) 0.0082(5)
Si4C 0.0266(6) 0.0201(6) 0.0247(6) 0.0013(5) -0.0003(5) -0.0016(4)
C4SI 0.0266(6) 0.0201(6) 0.0247(6) 0.0013(5) -0.0003(5) -0.0016(4)
N1 0.0294(12) 0.0244(12) 0.0196(11) 0.0008(9) 0.0063(9) 0.0028(9)
N2 0.040(2) 0.0158(15) 0.0307(18) 0.000 0.0133(15) 0.000
N3 0.0374(19) 0.0172(15) 0.0198(15) 0.000 -0.0009(13) 0.000
C1 0.0340(17) 0.0404(18) 0.045(2) 0.0042(16) 0.0058(15) 0.0077(14)
C2 0.045(2) 0.058(3) 0.052(2) -0.005(2) 0.0008(18) 0.0011(19)
C3 0.0362(19) 0.063(3) 0.040(2) -0.0041(18) 0.0005(15) 0.0030(17)
C4 0.048(2) 0.0393(18) 0.0384(19) 0.0018(15) -0.0036(16) 0.0051(16)
C5 0.046(2) 0.067(3) 0.041(2) 0.001(2) 0.0000(17) 0.001(2)
C6 0.049(2) 0.065(3) 0.059(3) 0.007(2) 0.005(2) 0.001(2)
C7 0.080(4) 0.065(3) 0.062(3) 0.012(3) 0.018(3) -0.011(3)
C8 0.042(2) 0.054(2) 0.044(2) 0.0142(18) 0.0103(16) 0.0120(17)
C9 0.054(3) 0.055(3) 0.088(4) -0.010(3) 0.003(2) 0.017(2)
C10 0.056(2) 0.0335(18) 0.0408(19) -0.0048(15) 0.0064(16) -0.0067(16)
C11 0.045(2) 0.058(2) 0.044(2) -0.0111(19) -0.0044(16) 0.0131(18)
C12 0.039(2) 0.067(3) 0.085(3) 0.045(3) 0.005(2) 0.007(2)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

230

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 N2 1.941(2) . ?
Cu1 N1 1.942(2) . ?
Cu1 Cu2 2.7064(8) . ?
Cu1 Cu1 2.7213(8) 2 ?
Cu1 Si1C 2.8936(19) . ?
Cu1 Si3C 2.9065(14) . ?
Cu2 N3 1.949(2) . ?
Cu2 N1 1.953(2) . ?
Cu2 Cu2 2.7176(9) 2 ?
Si1C C3 1.544(5) . ?
Si1C C2 1.565(5) . ?
Si1C N1 1.580(3) . ?
Si1C C1 1.615(5) . ?
Si1C Si2C 2.813(2) . ?
Si2C N1 1.712(3) . ?
Si2C C6 1.811(5) . ?
Si2C C4 1.811(4) . ?
Si2C C5 1.814(5) . ?
Si3C N2 1.647(2) . ?
Si3C C9 1.670(6) . ?
Si3C C7 1.679(6) . ?
Si3C C8 1.712(5) . ?
Si3C Si3C 2.811(3) 2 ?
Si4C C12 1.624(4) . ?
Si4C N3 1.657(2) . ?
Si4C C10 1.700(4) . ?
Si4C C11 1.718(5) . ?
Si4C Si4C 2.833(3) 2 ?
N2 C3SI 1.647(2) 2 ?
N2 Si3C 1.647(2) 2 ?
N2 Cu1 1.941(2) 2 ?
N3 C4SI 1.657(2) 2 ?
N3 Si4C 1.657(2) 2 ?
N3 Cu2 1.949(2) 2 ?
C1 H1A 0.97 . ?
C1 H1B 0.99 . ?
C1 H1C 0.97 . ?
C2 H2A 0.98 . ?
231

C2 H2B 0.99 . ?
C2 H2C 0.98 . ?
C3 H3A 0.99 . ?
C3 H3B 0.99 . ?
C3 H3C 0.97 . ?
C4 H4A 0.98 . ?
C4 H4B 0.98 . ?
C4 H4C 0.98 . ?
C5 H5A 0.98 . ?
C5 H5B 0.98 . ?
C5 H5C 0.97 . ?
C6 H6A 0.98 . ?
C6 H6B 0.98 . ?
C6 H6C 0.97 . ?
C7 H7A 0.98 . ?
C7 H7B 0.98 . ?
C7 H7C 0.99 . ?
C8 H8A 0.97 . ?
C8 H8B 0.99 . ?
C8 H8C 0.99 . ?
C9 H9A 0.97 . ?
C9 H9B 0.97 . ?
C9 H9C 0.98 . ?
C10 H10A 0.98 . ?
C10 H10B 0.97 . ?
C10 H10C 0.98 . ?
C11 H11A 0.98 . ?
C11 H11B 0.97 . ?
C11 H11C 0.98 . ?
C12 H12A 0.97 . ?
C12 H12B 0.97 . ?
C12 H12C 0.99 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 Cu1 N1 178.38(10) . . ?
N2 Cu1 Cu2 135.44(7) . . ?
N1 Cu1 Cu2 46.14(7) . . ?
232

N2 Cu1 Cu1 45.48(7) . 2 ?

N1 Cu1 Cu1 136.10(7) . 2 ?
Cu2 Cu1 Cu1 89.961(10) . 2 ?
N2 Cu1 Si1C 148.12(5) . . ?
N1 Cu1 Si1C 30.86(9) . . ?
Cu2 Cu1 Si1C 64.22(4) . . ?
Cu1 Cu1 Si1C 140.22(4) 2 . ?
N2 Cu1 Si3C 32.63(4) . . ?
N1 Cu1 Si3C 146.93(9) . . ?
Cu2 Cu1 Si3C 140.48(3) . . ?
Cu1 Cu1 Si3C 65.39(3) 2 . ?
Si1C Cu1 Si3C 151.81(5) . . ?
N3 Cu2 N1 178.33(10) . . ?
N3 Cu2 Cu1 135.84(7) . . ?
N1 Cu2 Cu1 45.81(7) . . ?
N3 Cu2 Cu2 45.80(7) . 2 ?
N1 Cu2 Cu2 135.84(7) . 2 ?
Cu1 Cu2 Cu2 90.039(10) . 2 ?
C3 Si1C C2 111.1(2) . . ?
C3 Si1C N1 111.9(2) . . ?
C2 Si1C N1 112.4(2) . . ?
C3 Si1C C1 107.9(2) . . ?
C2 Si1C C1 105.7(2) . . ?
N1 Si1C C1 107.3(2) . . ?
C3 Si1C Si2C 103.90(18) . . ?
C2 Si1C Si2C 87.90(18) . . ?
N1 Si1C Si2C 32.75(11) . . ?
C1 Si1C Si2C 137.42(17) . . ?
C3 Si1C Cu1 86.43(17) . . ?
C2 Si1C Cu1 151.48(19) . . ?
N1 Si1C Cu1 39.07(10) . . ?
C1 Si1C Cu1 88.80(15) . . ?
Si2C Si1C Cu1 65.55(5) . . ?
N1 Si2C C6 116.02(19) . . ?
N1 Si2C C4 109.22(16) . . ?
C6 Si2C C4 104.3(2) . . ?
N1 Si2C C5 112.20(16) . . ?
C6 Si2C C5 107.1(2) . . ?
C4 Si2C C5 107.5(2) . . ?
N1 Si2C Si1C 29.95(10) . . ?
C6 Si2C Si1C 93.09(16) . . ?
C4 Si2C Si1C 136.92(15) . . ?
C5 Si2C Si1C 104.37(15) . . ?
N2 Si3C C9 112.62(18) . . ?
233

N2 Si3C C7 114.1(2) . . ?
C9 Si3C C7 109.5(2) . . ?
N2 Si3C C8 107.80(18) . . ?
C9 Si3C C8 107.9(2) . . ?
C7 Si3C C8 104.5(2) . . ?
N2 Si3C Si3C 31.42(11) . 2 ?
C9 Si3C Si3C 104.50(19) . 2 ?
C7 Si3C Si3C 90.6(2) . 2 ?
C8 Si3C Si3C 136.77(14) . 2 ?
N2 Si3C Cu1 39.44(8) . . ?
C9 Si3C Cu1 86.43(16) . . ?
C7 Si3C Cu1 153.5(2) . . ?
C8 Si3C Cu1 89.80(14) . . ?
Si3C Si3C Cu1 64.30(4) 2 . ?
C12 Si4C N3 114.80(18) . . ?
C12 Si4C C10 107.5(2) . . ?
N3 Si4C C10 107.72(17) . . ?
C12 Si4C C11 109.4(2) . . ?
N3 Si4C C11 110.69(16) . . ?
C10 Si4C C11 106.3(2) . . ?
C12 Si4C Si4C 91.66(17) . 2 ?
N3 Si4C Si4C 31.27(11) . 2 ?
C10 Si4C Si4C 137.61(14) . 2 ?
C11 Si4C Si4C 102.00(15) . 2 ?
Si1C N1 Si2C 117.30(17) . . ?
Si1C N1 Cu1 110.08(16) . . ?
Si2C N1 Cu1 115.33(14) . . ?
Si1C N1 Cu2 114.68(16) . . ?
Si2C N1 Cu2 107.87(14) . . ?
Cu1 N1 Cu2 88.05(11) . . ?
C3SI N2 Si3C 0.00(12) 2 2 ?
C3SI N2 Si3C 117.2(2) 2 . ?
Si3C N2 Si3C 117.2(2) 2 . ?
C3SI N2 Cu1 115.82(6) 2 . ?
Si3C N2 Cu1 115.82(6) 2 . ?
Si3C N2 Cu1 107.93(6) . . ?
C3SI N2 Cu1 107.93(6) 2 2 ?
Si3C N2 Cu1 107.93(6) 2 2 ?
Si3C N2 Cu1 115.82(6) . 2 ?
Cu1 N2 Cu1 89.03(14) . 2 ?
Si4C N3 C4SI 117.5(2) . 2 ?
Si4C N3 Si4C 117.5(2) . 2 ?
C4SI N3 Si4C 0.00(11) 2 2 ?
Si4C N3 Cu2 112.48(6) . . ?
234

C4SI N3 Cu2 111.22(6) 2 . ?

Si4C N3 Cu2 111.22(6) 2 . ?
Si4C N3 Cu2 111.22(6) . 2 ?
C4SI N3 Cu2 112.48(6) 2 2 ?
Si4C N3 Cu2 112.48(6) 2 2 ?
Cu2 N3 Cu2 88.41(14) . 2 ?
Si1C C1 H1A 109.3 . . ?
Si1C C1 H1B 108.7 . . ?
H1A C1 H1B 109.4 . . ?
Si1C C1 H1C 109.3 . . ?
H1A C1 H1C 110.9 . . ?
H1B C1 H1C 109.3 . . ?
Si1C C2 H2A 110.2 . . ?
Si1C C2 H2B 110.7 . . ?
H2A C2 H2B 108.2 . . ?
Si1C C2 H2C 110.7 . . ?
H2A C2 H2C 108.8 . . ?
H2B C2 H2C 108.2 . . ?
Si1C C3 H3A 109.3 . . ?
Si1C C3 H3B 110.0 . . ?
H3A C3 H3B 107.7 . . ?
Si1C C3 H3C 111.0 . . ?
H3A C3 H3C 109.2 . . ?
H3B C3 H3C 109.5 . . ?
Si2C C4 H4A 109.8 . . ?
Si2C C4 H4B 109.6 . . ?
H4A C4 H4B 109.3 . . ?
Si2C C4 H4C 109.7 . . ?
H4A C4 H4C 109.3 . . ?
H4B C4 H4C 109.1 . . ?
Si2C C5 H5A 108.5 . . ?
Si2C C5 H5B 108.7 . . ?
H5A C5 H5B 109.9 . . ?
Si2C C5 H5C 108.9 . . ?
H5A C5 H5C 110.2 . . ?
H5B C5 H5C 110.6 . . ?
Si2C C6 H6A 109.0 . . ?
Si2C C6 H6B 108.8 . . ?
H6A C6 H6B 109.4 . . ?
Si2C C6 H6C 109.4 . . ?
H6A C6 H6C 110.2 . . ?
H6B C6 H6C 110.1 . . ?
Si3C C7 H7A 110.4 . . ?
Si3C C7 H7B 110.1 . . ?
235

H7A C7 H7B 109.9 . . ?

Si3C C7 H7C 109.3 . . ?
H7A C7 H7C 108.7 . . ?
H7B C7 H7C 108.4 . . ?
Si3C C8 H8A 110.1 . . ?
Si3C C8 H8B 109.3 . . ?
H8A C8 H8B 109.8 . . ?
Si3C C8 H8C 109.5 . . ?
H8A C8 H8C 109.9 . . ?
H8B C8 H8C 108.2 . . ?
Si3C C9 H9A 108.5 . . ?
Si3C C9 H9B 108.7 . . ?
H9A C9 H9B 110.8 . . ?
Si3C C9 H9C 108.0 . . ?
H9A C9 H9C 110.3 . . ?
H9B C9 H9C 110.5 . . ?
Si4C C10 H10A 108.8 . . ?
Si4C C10 H10B 109.2 . . ?
H10A C10 H10B 110.6 . . ?
Si4C C10 H10C 108.5 . . ?
H10A C10 H10C 109.3 . . ?
H10B C10 H10C 110.4 . . ?
Si4C C11 H11A 108.9 . . ?
Si4C C11 H11B 109.0 . . ?
H11A C11 H11B 110.2 . . ?
Si4C C11 H11C 108.7 . . ?
H11A C11 H11C 109.7 . . ?
H11B C11 H11C 110.2 . . ?
Si4C C12 H12A 109.6 . . ?
Si4C C12 H12B 109.1 . . ?
H12A C12 H12B 111.2 . . ?
Si4C C12 H12C 108.0 . . ?
H12A C12 H12C 109.7 . . ?
H12B C12 H12C 109.2 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
236

_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 Cu1 Cu2 N3 0.09(5) . . . . ?
N1 Cu1 Cu2 N3 179.60(12) . . . . ?
Cu1 Cu1 Cu2 N3 0.07(3) 2 . . . ?
Si1C Cu1 Cu2 N3 148.69(5) . . . . ?
Si3C Cu1 Cu2 N3 -48.99(6) . . . . ?
N2 Cu1 Cu2 N1 -179.51(12) . . . . ?
Cu1 Cu1 Cu2 N1 -179.53(12) 2 . . . ?
Si1C Cu1 Cu2 N1 -30.90(13) . . . . ?
Si3C Cu1 Cu2 N1 131.42(13) . . . . ?
N2 Cu1 Cu2 Cu2 0.06(3) . . . 2 ?
N1 Cu1 Cu2 Cu2 179.57(12) . . . 2 ?
Cu1 Cu1 Cu2 Cu2 0.04(2) 2 . . 2 ?
Si1C Cu1 Cu2 Cu2 148.67(5) . . . 2 ?
Si3C Cu1 Cu2 Cu2 -49.01(6) . . . 2 ?
N2 Cu1 Si1C C3 -45.5(2) . . . . ?
N1 Cu1 Si1C C3 132.1(2) . . . . ?
Cu2 Cu1 Si1C C3 178.32(18) . . . . ?
Cu1 Cu1 Si1C C3 -127.23(16) 2 . . . ?
Si3C Cu1 Si1C C3 22.5(2) . . . . ?
N2 Cu1 Si1C C2 -175.4(4) . . . . ?
N1 Cu1 Si1C C2 2.1(4) . . . . ?
Cu2 Cu1 Si1C C2 48.4(4) . . . . ?
Cu1 Cu1 Si1C C2 102.8(4) 2 . . . ?
Si3C Cu1 Si1C C2 -107.5(4) . . . . ?
N2 Cu1 Si1C N1 -177.57(19) . . . . ?
Cu2 Cu1 Si1C N1 46.22(15) . . . . ?
Cu1 Cu1 Si1C N1 100.68(16) 2 . . . ?
Si3C Cu1 Si1C N1 -109.63(18) . . . . ?
N2 Cu1 Si1C C1 62.6(2) . . . . ?
N1 Cu1 Si1C C1 -119.9(2) . . . . ?
Cu2 Cu1 Si1C C1 -73.64(16) . . . . ?
Cu1 Cu1 Si1C C1 -19.19(18) 2 . . . ?
Si3C Cu1 Si1C C1 130.51(17) . . . . ?
N2 Cu1 Si1C Si2C -152.50(13) . . . . ?
N1 Cu1 Si1C Si2C 25.07(15) . . . . ?
Cu2 Cu1 Si1C Si2C 71.29(4) . . . . ?
Cu1 Cu1 Si1C Si2C 125.75(5) 2 . . . ?
Si3C Cu1 Si1C Si2C -84.56(11) . . . . ?
C3 Si1C Si2C N1 -109.0(2) . . . . ?
C2 Si1C Si2C N1 139.7(3) . . . . ?
C1 Si1C Si2C N1 28.5(3) . . . . ?
Cu1 Si1C Si2C N1 -29.57(16) . . . . ?
237

C3 Si1C Si2C C6 32.8(2) . . . . ?

C2 Si1C Si2C C6 -78.5(3) . . . . ?
N1 Si1C Si2C C6 141.8(2) . . . . ?
C1 Si1C Si2C C6 170.3(3) . . . . ?
Cu1 Si1C Si2C C6 112.24(17) . . . . ?
C3 Si1C Si2C C4 -82.0(3) . . . . ?
C2 Si1C Si2C C4 166.7(3) . . . . ?
N1 Si1C Si2C C4 27.0(3) . . . . ?
C1 Si1C Si2C C4 55.5(3) . . . . ?
Cu1 Si1C Si2C C4 -2.5(2) . . . . ?
C3 Si1C Si2C C5 141.3(2) . . . . ?
C2 Si1C Si2C C5 30.0(2) . . . . ?
N1 Si1C Si2C C5 -109.7(2) . . . . ?
C1 Si1C Si2C C5 -81.2(3) . . . . ?
Cu1 Si1C Si2C C5 -139.24(15) . . . . ?
N1 Cu1 Si3C N2 -177.12(18) . . . . ?
Cu2 Cu1 Si3C N2 100.56(13) . . . . ?
Cu1 Cu1 Si3C N2 44.38(12) 2 . . . ?
Si1C Cu1 Si3C N2 -114.82(16) . . . . ?
N2 Cu1 Si3C C9 133.1(2) . . . . ?
N1 Cu1 Si3C C9 -44.1(2) . . . . ?
Cu2 Cu1 Si3C C9 -126.39(19) . . . . ?
Cu1 Cu1 Si3C C9 177.4(2) 2 . . . ?
Si1C Cu1 Si3C C9 18.2(2) . . . . ?
N2 Cu1 Si3C C7 4.5(4) . . . . ?
N1 Cu1 Si3C C7 -172.6(4) . . . . ?
Cu2 Cu1 Si3C C7 105.1(4) . . . . ?
Cu1 Cu1 Si3C C7 48.9(4) 2 . . . ?
Si1C Cu1 Si3C C7 -110.3(4) . . . . ?
N2 Cu1 Si3C C8 -119.04(19) . . . . ?
N1 Cu1 Si3C C8 63.8(2) . . . . ?
Cu2 Cu1 Si3C C8 -18.48(16) . . . . ?
Cu1 Cu1 Si3C C8 -74.66(14) 2 . . . ?
Si1C Cu1 Si3C C8 126.14(17) . . . . ?
N2 Cu1 Si3C Si3C 25.08(12) . . . 2 ?
N1 Cu1 Si3C Si3C -152.04(15) . . . 2 ?
Cu2 Cu1 Si3C Si3C 125.64(4) . . . 2 ?
Cu1 Cu1 Si3C Si3C 69.46(5) 2 . . 2 ?
Si1C Cu1 Si3C Si3C -89.74(12) . . . 2 ?
C3 Si1C N1 Si2C 81.6(2) . . . . ?
C2 Si1C N1 Si2C -44.4(3) . . . . ?
C1 Si1C N1 Si2C -160.2(2) . . . . ?
Cu1 Si1C N1 Si2C 134.5(2) . . . . ?
C3 Si1C N1 Cu1 -53.0(2) . . . . ?
238

C2 Si1C N1 Cu1 -178.9(2) . . . . ?

C1 Si1C N1 Cu1 65.2(2) . . . . ?
Si2C Si1C N1 Cu1 -134.5(2) . . . . ?
C3 Si1C N1 Cu2 -150.3(2) . . . . ?
C2 Si1C N1 Cu2 83.7(3) . . . . ?
C1 Si1C N1 Cu2 -32.1(2) . . . . ?
Si2C Si1C N1 Cu2 128.1(2) . . . . ?
Cu1 Si1C N1 Cu2 -97.36(19) . . . . ?
C6 Si2C N1 Si1C -43.4(3) . . . . ?
C4 Si2C N1 Si1C -160.81(19) . . . . ?
C5 Si2C N1 Si1C 80.1(2) . . . . ?
C6 Si2C N1 Cu1 88.8(2) . . . . ?
C4 Si2C N1 Cu1 -28.6(2) . . . . ?
C5 Si2C N1 Cu1 -147.67(17) . . . . ?
Si1C Si2C N1 Cu1 132.2(2) . . . . ?
C6 Si2C N1 Cu2 -174.69(19) . . . . ?
C4 Si2C N1 Cu2 67.88(18) . . . . ?
C5 Si2C N1 Cu2 -51.2(2) . . . . ?
Si1C Si2C N1 Cu2 -131.3(2) . . . . ?
N2 Cu1 N1 Si1C 52(3) . . . . ?
Cu2 Cu1 N1 Si1C -115.62(19) . . . . ?
Cu1 Cu1 N1 Si1C -114.94(14) 2 . . . ?
Si3C Cu1 N1 Si1C 125.37(16) . . . . ?
N2 Cu1 N1 Si2C -83(3) . . . . ?
Cu2 Cu1 N1 Si2C 108.88(18) . . . . ?
Cu1 Cu1 N1 Si2C 109.56(13) 2 . . . ?
Si1C Cu1 N1 Si2C -135.5(2) . . . . ?
Si3C Cu1 N1 Si2C -10.1(2) . . . . ?
N2 Cu1 N1 Cu2 168(3) . . . . ?
Cu1 Cu1 N1 Cu2 0.68(17) 2 . . . ?
Si1C Cu1 N1 Cu2 115.62(19) . . . . ?
Si3C Cu1 N1 Cu2 -119.01(11) . . . . ?
N3 Cu2 N1 Si1C -59(3) . . . . ?
Cu1 Cu2 N1 Si1C 111.2(2) . . . . ?
Cu2 Cu2 N1 Si1C 110.64(15) 2 . . . ?
N3 Cu2 N1 Si2C 74(3) . . . . ?
Cu1 Cu2 N1 Si2C -116.03(17) . . . . ?
Cu2 Cu2 N1 Si2C -116.64(11) 2 . . . ?
N3 Cu2 N1 Cu1 -170(3) . . . . ?
Cu2 Cu2 N1 Cu1 -0.61(17) 2 . . . ?
C9 Si3C N2 C3SI 80.7(2) . . . 2 ?
C7 Si3C N2 C3SI -44.89(19) . . . 2 ?
C8 Si3C N2 C3SI -160.45(17) . . . 2 ?
Si3C Si3C N2 C3SI 0.0 2 . . 2 ?
239

Cu1 Si3C N2 C3SI 132.89(9) . . . 2 ?

C9 Si3C N2 Si3C 80.7(2) . . . 2 ?
C7 Si3C N2 Si3C -44.89(19) . . . 2 ?
C8 Si3C N2 Si3C -160.45(17) . . . 2 ?
Cu1 Si3C N2 Si3C 132.89(9) . . . 2 ?
C9 Si3C N2 Cu1 -52.2(3) . . . . ?
C7 Si3C N2 Cu1 -177.8(2) . . . . ?
C8 Si3C N2 Cu1 66.66(18) . . . . ?
Si3C Si3C N2 Cu1 -132.89(9) 2 . . . ?
C9 Si3C N2 Cu1 -150.1(2) . . . 2 ?
C7 Si3C N2 Cu1 84.4(2) . . . 2 ?
C8 Si3C N2 Cu1 -31.2(2) . . . 2 ?
Si3C Si3C N2 Cu1 129.24(11) 2 . . 2 ?
Cu1 Si3C N2 Cu1 -97.9(2) . . . 2 ?
N1 Cu1 N2 C3SI -58(3) . . . 2 ?
Cu2 Cu1 N2 C3SI 109.47(13) . . . 2 ?
Cu1 Cu1 N2 C3SI 109.50(13) 2 . . 2 ?
Si1C Cu1 N2 C3SI -7.9(2) . . . 2 ?
Si3C Cu1 N2 C3SI -133.6(2) . . . 2 ?
N1 Cu1 N2 Si3C -58(3) . . . 2 ?
Cu2 Cu1 N2 Si3C 109.47(13) . . . 2 ?
Cu1 Cu1 N2 Si3C 109.50(13) 2 . . 2 ?
Si1C Cu1 N2 Si3C -7.9(2) . . . 2 ?
Si3C Cu1 N2 Si3C -133.6(2) . . . 2 ?
N1 Cu1 N2 Si3C 76(3) . . . . ?
Cu2 Cu1 N2 Si3C -116.93(11) . . . . ?
Cu1 Cu1 N2 Si3C -116.90(11) 2 . . . ?
Si1C Cu1 N2 Si3C 125.72(10) . . . . ?
N1 Cu1 N2 Cu1 -167(3) . . . 2 ?
Cu2 Cu1 N2 Cu1 -0.031(16) . . . 2 ?
Si1C Cu1 N2 Cu1 -117.38(13) . . . 2 ?
Si3C Cu1 N2 Cu1 116.90(11) . . . 2 ?
C12 Si4C N3 C4SI -45.64(17) . . . 2 ?
C10 Si4C N3 C4SI -165.33(16) . . . 2 ?
C11 Si4C N3 C4SI 78.83(16) . . . 2 ?
Si4C Si4C N3 C4SI 0.0 2 . . 2 ?
C12 Si4C N3 Si4C -45.64(17) . . . 2 ?
C10 Si4C N3 Si4C -165.33(16) . . . 2 ?
C11 Si4C N3 Si4C 78.83(16) . . . 2 ?
C12 Si4C N3 Cu2 85.4(2) . . . . ?
C10 Si4C N3 Cu2 -34.31(19) . . . . ?
C11 Si4C N3 Cu2 -150.15(17) . . . . ?
Si4C Si4C N3 Cu2 131.02(10) 2 . . . ?
C12 Si4C N3 Cu2 -177.24(18) . . . 2 ?
240

C10 Si4C N3 Cu2 63.07(17) . . . 2 ?

C11 Si4C N3 Cu2 -52.8(2) . . . 2 ?
Si4C Si4C N3 Cu2 -131.60(10) 2 . . 2 ?
N1 Cu2 N3 Si4C -78(3) . . . . ?
Cu1 Cu2 N3 Si4C 112.32(12) . . . . ?
Cu2 Cu2 N3 Si4C 112.35(12) 2 . . . ?
N1 Cu2 N3 C4SI 56(3) . . . 2 ?
Cu1 Cu2 N3 C4SI -113.58(12) . . . 2 ?
Cu2 Cu2 N3 C4SI -113.55(11) 2 . . 2 ?
N1 Cu2 N3 Si4C 56(3) . . . 2 ?
Cu1 Cu2 N3 Si4C -113.58(12) . . . 2 ?
Cu2 Cu2 N3 Si4C -113.55(11) 2 . . 2 ?
N1 Cu2 N3 Cu2 170(3) . . . 2 ?
Cu1 Cu2 N3 Cu2 -0.031(16) . . . 2 ?
_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full
32.0
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max 0.998
_refine_diff_density_min -1.153
_refine_diff_density_rms 0.137
# END OF CIF

241

Appendix B
Phosphorescence Spectra of Cu(I) Amides

Intensity (arbitrary units)

1.0

0.8

0.6
300 K
77 K

0.4

0.2

0.0
400

450

500

550

600

650

/nm

Fig. B-1. Corrected Phosphorescence Spectra Of Solid

[CuN(SiMe3)2]4, With 310 nm Excitation.

242

Intensity (arbitrary units)

1.0

0.8

0.6

0.4

300 K
77 K

0.2

0.0
400

450

500

550

600

650

700

/nm

Figure B-2. Corrected Phosphorescence Spectra Of Solid

[CuN(t-Bu)(SiMe3)]4 (Green Luminescent Material), With 295 nm Excitation.

243

Intensity (arbitrary units)

1.0

0.8

0.6

0.4

300 K
77 K

0.2

0.0
450

500

550

600

650

/nm

Figure B-3. Corrected Phosphorescence Spectra Of Solid [CuN(t-Bu)(SiMe3)]n

(Orange Luminescent Material), With 310 and 295 nm Excitation
(300 K And 77 K Spectra, Respectively).

244

Intensity (arbitrary units)

1.0

0.8

0.6

0.4

300 K
77 K

0.2

0.0
450

500

550

600

650

/nm

Figure B-4. Corrected Phosphorescence Spectra Of Solid

[CuN(i-Pr)2]4, With 305 nm Excitation.

245

Intensity (arbitrary units)

1.0

0.8

0.6

0.4

300 K
77 K

0.2

0.0
450

500

550

600

650

/nm

Figure B-5. Corrected Phosphorescence Spectra Of Solid [CuNEt2]4, With 330 And
320 nm Excitation (300 K And 77 K Spectra, Respectively).

246

Vita
Muna BuFaroosha was born on April 18, 1967, to Saif and Fatama BuFaroosha
in Dubai, United Arab Emirates. She attended United Arab Emirates University where
she received her Bachelor of Science degree in chemistry in May of 1989. She attended
Michigan State University where she received her Master of Science degree in
chemistry in May 1995. In 1996 she began her Ph.D. study at Louisiana State
University and will receive the degree of Doctor of Philosophy in August 2002.
Currently, she is a teaching assistant in United Arab Emirates University. She is on
leave from her position at UAE University.

247